Schemes With Classification-Final

Schiff bases form complexes with various metals like Sn, Ni, Zn, Ln etc in both deprotonated
and neutral forms. With the neutral forms of Schiff bases, adducts are formed by reactions in
alcoholic media, (14a-14c,). While deprotonated Schiff bases are formed in the presence of a
base such as alkoxide ion or by the exchange reaction (14d-14e, 34a-34b, 35a) (AA1). However,
few other complexes are also reported by reactions in alcoholic media without the presences of
auxiliary bases (…….)
Previous literature reports have demonstrated that Schiff bases derived from o-vanillin are
biologically more significant due to their superior chelating ability, structural flexibility [1] and
diverse biological activities. The presence of different substituents in o-vanillin derived ligands
(to form binary complexes like 14,95,96,1,15,2,34,35, ) or additional co-ligands (to form ternay
complexes like 140,144,42, ) can create interesting variations in coordination sphere, space
configuration and in the electron density distribution around transition metal / simply metal
complexes, which not only influence their spectral properties but provide an active
pharmacophore scaffold for the design of chemotherapeutic drugs by changing in metabolic path
ways or its relative activities, as well as in the binding mechanism of metal complexes to DNA.
o-vanillin forms Schiff bases with Hb (hemoglobin) amino groups, particularly the terminal
α1val, and thereby increases its oxygen affinity, and thereby reducing polymerization and RBC
sickling. o-vanillin also directly affects RBC membrane permeability. o-vanillin also directly
inhibits the main cation pathways which contribute towards dehydration of HbS-containing
RBCs [2].
o -Vanillin ( Figure 1 ) is used as an important pharmaceutical intermediate for the treatment of
bellyaches and in spicery. o –Vanillin also has antioxidant activity, due to their ability to capture
free radicals. This behavior is related to the presence of the OH moiety in their structure
[3].
O-vanillin as multidentate ligand has allowed the construction of polymers with defined
geometry and special properties. From the structure point of view, the o-vanillin ligand has three
1
oxygen donor atoms, (one phenoxide, one aldehydic and one methoxide oxygen) which exhibit
suitable relative positions to coordinate metal centers in following three ways [4].
Figure : Co-ordination mode of o-vanillin
On chelation the polarity of the metal ion reduced to a greater extent due to the overlap of the
ligand orbital and partial sharing of positive charges of metal ion with donor groups. It was
further noted that the delocalization of electrons over the whole chelate ring enhanced the
lipophillicity of the complexes. This increased lipophillicity enhances the penetration of the
complexes into lipid membrane and blocking the metal sites on enzymes of microorganism.
(V67).
polynuclear metal complexes, also known as coordination clusters (CCs),
The signals due to aromatic protons shifted downfield in the complexes because of deshielding
due to transfer of electron density from ring to metal atom
The ligand design plays a decisive role in transporting and addressing the molecule to the target,
resisting untimely exchanges with biomolecules.
A large number of chemotherapeutic agents and cytokines (particularly complexes) imply

potentially useful therapeutic strategies and elicit antitumor effect by inducing cancer cell
apoptosis by generating large amount of noxious radicals into the cancer cells. SOD can
putatively participate in such apoptotic events leading to tumor reduction and cell proliferation.
2
There are several limitations of metal complexes as a pharmacological agent, including high
cost, low lipid solubility, low penetration into cells, immunogenicity, and lability to gastric and
intestinal proteases. In this regard therapeutic agents that pertains to stable, less toxic and more
effective metallic component like Cu(II) are of particular interest and include a plethora of
compounds: antitumor, antioxidant, antimicrobial and antiflammatory agents and
radioprotectants.
Copper :-
The appropriate redox property of Cu(II) / metals is essential for various metabolic pathways like
mitochondrial respiration, free radical scavenging, and iron absorption where it acts as a catalytic
cofactor. The Cu(II) / metal complexes follows different mode of action towards DNA (non-
covalent) as compared to cisplatin (covalent). Therefore, Cu(II)-based generic complexes exhibit
higher antineoplastic potency towards human ovarian carcinoma (CH1), murine leukaemia
(L1210), and various cervicouterine carcinomas as compared to cisplatin.
Copper plays a pivotal role in cell physiology as a catalytic cofactor in the redox chemistry of
mitochondrial respiration, iron absorption, free radical scavenging and elastin crosslinking. For
the function of several enzymes and proteins involved in energy metabolism, respiration and
DNA synthesis, copper is very essential.
Copper is an essential trace metal and regulates angiogenesis, i.e., the growth of tumor blood
vessels that are important for tumor growth, invasion, and metastasis. Accumulation of high
concentration of copper is an unique feature of cancer cells, which while leaving normal cells to
suffer only minimally thereby converting pro-angiogenic cofactor copper into a cancer-specific
killing agent.
Zinc :-
Zinc is a biocompatible metal with a high coordination ability, interesting photophysical
properties and promising for inorganic pharmaceuticals as radioprotective agents and antidiabetic
insulin-mimetics.9 Organotin(IV) complexes exhibited anticancer activity, lower general
toxicity, better body clearance, less side effects, and no emetogenesis.
Zinc is the second most abundant transition metal in the human body. Its metal complexes
exhibit considerable scavenging activity than the ligand 34b
3
Organotin :-
Organotin complexes induces cytotoxicity as a consequence of their mechanism of action viz.,
macromolecular synthesis inhibition, mitochondrial energy metabolism, and reduction of DNA
synthesis, as well as the cell membrane direct interaction (increasing cytosolic Ca2+
concentration). In vivo studies showed an elevation in oxidative and DNA damage. In the
antiproliferative activity of organotins, increased histone acetyltransferase activity and activation
of retinoid X receptor and PPARg may play surplus roles. Therefore, organotin(IV) compounds
appear very promising as potential drugs and may result in compounds that are particularly
active against cisplatin- resistant cancers.
Organotin(IV) compounds have demonstrated remarkable in vitro and in vivo biocidal activity as
having antiproliferative, antifungal, antimicrobial, antitumor activities. Actually organotin(IV)
moieties bound preferentially to a phosphate group of the DNA backbone. Additionally, it has
also been established that organotin(IV) are involved in cancer chemotherapy because of their
apoptotic inducing property.
The biocidal (biochemical) activity of ligands enhance upon chelation with suitable metal ions
due to an increase in their target oriented nature.
Organotin(IV) complexes with Schiff base ligands have received considerable attention owing to
their fascinating chemical behavior, kinetically stable, relatively lipophilic nature and possessing
attractive properties such as lower toxicity than platinum drugs. Usually, phenyl- and n-
butyltin(IV) complexes display a larger array of biological activity than their methyl-, hexyl- or
octyltin(IV) analogs.
Ruthenium:-
Ruthenium Schiff’s base complexes, particularly those containing oxygen and nitrogen as donor
atoms have been found to be very efficient catalysts in the oxidation of alcohols and alkenes (3a-
3c), antineoplastic properties of ruthenium complexes. cis-[RuCl2(DMSO)4] complex is involved
in chemoselective cleavage of the C=N bond of the Schiff bases.
Molybdenum :-
dinitrosylmolybdenum(0) complexes are used as homogeneous catalysts.
Ln Series :-
Lanthanide complexes functioning as single-molecule magnets (SMMs) have flourished and
become increasingly interesting in the field of nanomagnetic materials. In present, the best
4
candidate of these molecular materials is Dy III ion due to the inherent strong spin-orbital coupling
effect and hence very large magnetic anisotropy of the 6H15/2 ground state.
4f-based polynuclear compounds are highly promising systems for the development of higher-
barrier SMMs because of their significant magnetic anisotropy arising from the strong spin-orbit
coupling in low-symmetry crystal fields.
Ln(NO3)3. 6H2O (Ln = Pr, Nd, Er ) were prepared by dissolving Pr 6O11, Nd2O3 and Er2O3 ( 99.95
% ) in concentrated nitric acid and crystallizing the salts by evaporating the solution on a steam
bath.
Ln3+ (Nd3+, Yb3+ or Er3+) complexes, with long-lived and characteristic linelike near-infrared
(NIR) emission bands, have attracted much attention due to their potential applications in
fluoroimmunoassay, materials for optical telecommunication or organic light-emitting diodes
(OLEDs).(V145)
The Cl ion in the complex can enhances the antibacterial activity due to the killing microbes or
inhibiting their multiplication by blocking their active site
o-vanillin- Ni complex (figure number from intro) show good magnetic property.
Uranium :-
The Schiffbase complexes of uranium have aroused interest on account of their high stability,
usefulness in selective chemical separations and their formation in higher coordination numbers.
The rationally designed ligands promote ferromagnetic interaction via strong spin–orbit coupling
of the metal ions like 3d/4f metals. These interactions are attained by the overlap of bridging
ligand orbitals with the 3d/4f orbitals of the metal ions. It may result in various mono- and
polynuclear systems to show slow magnetic relaxation effects and plays a much more important
role in the pursuit of single-molecule magnet (SMM) with higher anisotropic barriers. These
SMM have great potential applications in data storage, quantum computing and spintronics at the
molecular level,
5
The self-assembly process of metal complexes of d10 metal ions has grown into a very active
research area, because they exhibit interesting structural features and potential applications in
light-emitting diodes, gene expression, apoptosis, enzyme regulation, neurotransmission,
fluorescence imaging, and cancer phototherapy.
Table 1: IR data for Metal-Oxygen & Metal-Nitrogen Coordination in Complexes

Complex ν (M-O) IR Values ν (M-N) IR Values
14a-14e, 15a-15e, 16d-16h, 34a, 34b, 35a, 35c, 95a-95c, Sn-O 470-654 Sn-N 447-499
96a-96g, 140e-140h,
12a, 13j, 23a, 24a, 32d, 52a, 53a, 56b, 67b, 69a, 77a, Cu-O 410-690 Cu-N 400-615
84a, 86a, 89c, 90c, 92c, 97a, 98a, 99e, 101b, 103d,
106c, 116b, 117b, 118b, 140a-140d, 144a, 144f, 146a-
146c, 147a, 150a,153a.154a, 155a 157d, 165b, 167a,
175a, 177a, 182c, 183d, 185c
1f, 12b, 23c, 32e, 56a, 67a, 69d, 77f, 86e, 90b, 92b, Zn-O 328-645 Zn-N 419-584
94c, 98e, 99f, 101d, 103e, 106b, 132c, 144b, 144g, 145a,
150b, 151a-152a, 153b,154b, 157e, 175c, 183e
12d, 35b, 99a, 197a, 198, 203c Fe-O 415-851 Fe-N 450-570
16c Mo-O 911-938
173a, 180e Pr-O 380-488 Pr-N 500
26c, 173e, 175e, 180f, Nd-O 400-560 Nd-N 454-480
173c Er-O 490
3a, 52b, 53b, 97b, 188a, 189a, 190a Ru-O 503-740 Ru-N 400-490
5a, 12c, 13i, 23b, 32c, 56c, 69c, 77c, 86b, 89d, 90d, Ni-O 333-628 Ni-N 390-611
92d, 94b, 98d, 99d, 100a, 101c, 102c, 104a, 106a, 116c,
117c, 118c, 119c, 132b, 144e, 157c, 175b, 177b, 182b,
183c, 185b
8a, 16i, 23e, 86g, 175g, 177e U-O 447-530 U-N 400-536
10a ClO4- 623-1099

12f, 32a, 35a, 86d, 89b, 98b, 99b, 102b, 183a Mn-O 371-554 Mn-N 425-580
12e, 23d, 24b, 32b, 69b, 77b, 86c, 89a, 90a, 92a, 94a, Co-O 345-728 Co-N 410-617
98c, 99c, 101a, 102a, 103c, 116a, 117a, 118a, 132a,
144d, 157b, 175d, 177c, 182a, 183b, 185a
13a, 26a, 164a, 180c La-O 380-480 La-N 420-560
13b, 26b, 180d Ce-O 350-375 Ce-N 435-450
13c, 86f Sm-O 370-520 Sm-N 410-500
13d Eu-O 380 Eu-N 500
77e, 144c, 177d V-O 412-465 V-N 480-540
13e, 26e, 164b Gd-O 420-480 Gd-N 420-560
13f Dy-O 400 Dy-N 480
175f Th-O 540 Th-N 460
6
32f, 77d, 98f, 100b Pd-O 405-480 Pd-N 487-567
89e, 99g, 103f Cd-O 450-646 Cd-N 435-553
69e Pb-O 540-588 Pb-N 428-459
75a Si-O 1070-1080
185d Cr-O 580 Cr-N 480
Table : Activity Data of Homometallic Complexes

Complex Microbial Strains
Active Against 3a-3c, 4a-4b, 14a-14e, 24a- Bacillus cereus, Bacillus cirroglagellous, Bacillus
Bacterial 24b, 32b, 32d, 39b, 52a, 52b, amyloliquefaciens, Bacillus subtilis subsp. spizizenii,
Strains 53a, 53b, 56, 56a-56c, 67b, Staphylococcus aureus, Escherichia coli, Klebsiella aerogen,
83a, 90a-90d, 92a-92d, 97a, Klebsiella pneumonia, Salmonella typhimurium, Salmonella
97b, 99a-99g, 101a-101d, arizonae, Salmonella typhi, Enterobacter cloacae,
102a-102d, 103a-103b, Chromobacterium violaceum, Proteus vulgaris, Serratia
106a-106c, 119g, 140b, marcescens, Micrococcus luteus, Pseudomonas aeruginosa,
144a, 144b, 145a, 157a- Pseudomonas mendocina, Staphylococcus epidermidis,
157e, 157d, 164a-164b, Mycobacterium tuberculosis,
165b, 167a, 173q-173u,
176a-176c, 177a-177e, 180b,
181c, 183a-183e, 185a-185d,
187b, 188a, 189a, 190a,
Active Against 34e, 90a-90d, 92a-92d, 99a- Fusarium solani, Fusarium oxysporum, Aspergillus niger.
Fungal Strains 99g, 101a-101d, 102a-102d, Aspergillus terreus, Aspergillus flavus, Aspergillus fumigatus,
106a-106c, 145a, 165a, Candida albicans, Candida kefyr, Saccharomyces cerevisiae,
168b-168d, 177a-177d, Cryptococcus neoformans, Penicillium chrysogenum,
140b, 180b, 185a-185d, Rhizoctonia solani
187b, 191a, 192a, 193a,
Antiproliferati 15a, 15c, 15e, 144a-144b DNA/BSA interaction, anti-proliferative effect on Huh7 cell
ve Effects line
Antitumor/ 15a, 15c, 15e, 16f, 16g, 25a, Antitumor lymphocytic leukemia cells, anticancer, human
anticancer 43a, 92c, 140a-140c, 144a- carcinoma cell lines (K562, MCF7, HT29, HCT15, SW620,
144b, 146a-146d, 157a- SiHa, T24, A498, 786-O, MIAPACA2 ,Hop-62, PC3, DWD,
157e, 164a-164b, 167a, A549), 786-O (human carcinoma cell lines), HL-60, A549,
170a-170b, 176a-176c HT-29, HCT-116 & Caco-2 (human carcinoma cell lines),
Anti-tumor (MCF-7 cell line), human lung carcinoma cells
(A549 cells), human colorectal carcinoma cells (COLO 205
cells), human hepatocellular carcinoma cells (PLC5 cells) and
human fibroblasts cells (NIH3T3), tumor cell proteasome,
antineoplastic, breast cancer and leukemia cells, breast cancer
cell lines (MCF-7), HepG2 hepatocellular carcinoma cell line
Miscellaneous 12a, 12e, 12f, 16, 34b, 34c, depress the metabolism of Stenostigma remota, O2˙ˉ
34f, 52a, 52b, 53a, 53b, 55a, scavenging activity, Anti-tuberculosis, free radical scavenger
55d, 56, 56a-56c, 101a-101d activity, Cytotoxin activity, antioxidant, sensor for E.coli and
, 102a-102d, 107a, 134a- Staphylococcus aureus, insulin-like activity, cell-differentiation
134b , 135a-135b, 136a- biological activity, growth-inhibitory activity, structure-specific
136b , 140b, 146a-146d, bioactivity selection, fine-tuning zinc insulin-like activity, zinc-
167a induced adipogenesis, biomolecular correlations,
7
Saccharomyces cereviaceae,, DNA Cleavage Activity
1- Hydrazides / Semicarbazones
Aroylhydrazones entailing o-vanillin can be involved in keto-enol tautomeric interconversion

(Figure-1). Tautomeric equilibrium can also involve aldehyde moiety if the hydroxyl group is
situated in ortho position with respect to the C=N double bond (Structure-C) The tautomeric
interconversion, i.e. isomerization of hydrazones due to solvent effect, pH value or UV
irradiation can also occur (Structures A-C)
Different tautomeric and isomeric forms have different spectral properties and can be
distinguished according to their IR, UV–Vis and NMR spectra. Since A-C isomers can have
diverse chelating properties as well as pharmacodynamics activities, the study of such an
equilibrium is relevant not only from the theoretical point of view, but for further development of
aroylhydrazones as potential drug candidates.
Tautomeric interconversion (A-C) is possible and can facilitate complexation with that of metal
cations. But A & B can easily form chelates. As a consequence, aroylhydrazones act as doubly
deprotonated, tridentate O,N,O donors in B .
In HNMR spectra of compounds in DMSO strong deshielding of hydroxyl protons (δ≈12.2 ppm)
due to intramolecular hydrogen bonds was recorded. The signals at 10.79–11.14 ppm assigned to
NH protons indicate hydrogen bond formation between solvent molecules and the amide proton.
That bond was stronger in acetone, causing a downfield shift of the -NH signals to 11.43 ppm. In
chloroform, the signal of amide proton appeared at 9.54 ppm since there is no possibility of H-
bond formation. In methanol, signals of both acidic -OH and -NH protons were missing,
confirming the proposed assignment. The signal of azomethine protons of A and B at ≈8.66 ppm
in DMSO confirmed the two tautomeric configurations of aroylhydrazones. The signal was
missing in C.
Furthermore, the addition of protic polar solvents like water can cause the ketoamine–enolimine
tautomeric interconversion from form A-C, which is usually accompanied by the appearance of a
new band in the spectral region around 400 nm.
8
in pure, DMSO hydrazones exist as E isomers in ketoamine form with respect to the hydrazide
part, and enolimine with respect to the aldehyde part of the molecules. Preference of the obtained
form is attributed to the p–p conjugation between p-electrons of the C=N bond and the lone
electron pair of the nitrogen of the C=N-N group. Also water had been considered responsible
for tautomerism as well as for isomerism of the structurally related compounds. While increasing
the water content, obtained spectral changes implied hydrogen bonding of aroylhydrazones
through the amide and hydroxyl groups with water molecules. It is very likely that formed
intermolecular hydrogen bonds additionally contributed to the stability of the ketoamine form.
(A) The same structural form revealed in diluted and nearly saturated solutions indicated that
concentration of the hydrazones did not affect equilibria in solution.
A B C
R = substituted or non-substituted Alkyl or Aryl groups
Figure-1 : Possible tautomeric forms of aroylhydrazones and E/Z configuration with respect
to the C=N double bond
1.1. Mode of Coordination of Mononuclear Ligands :-
The hydrazones derived from the diketo hydrazides (4) are a special group in the Schiff base
compounds because they possess (C=N), two (C=O) and other groups as a donor sites. The
multiplicity of donor sites make them more flexible that can form different modes of chelation
with transition metal ions and then several applications can be carried out.
Semicarbazones have wide range of medicinal properties and novel structural characteristics.
9
The o-vanillin based tridentate ligands can coordinate to the metal center via imino nitrogen,
deprotonated hydroxyl / phenolic oxygen and deprotonated enolic hydroxyl or carbonyl oxygen
in neighborhood. It results in the formation of either monobasic bidentate (1c, 1d, 4b, 5a) ,
monobasic tridentate (1b ((Me2Sn[3-(OMe)-2-OC6H3CH=N–N=C(O)Ph])), 4a, 13a-13f
(Ln(L13).X.nH2O), ) or dibasic tridentate (1a ((n-Bu)2Sn[3-(OMe)-2-OC6H3CH=N–N=C(O)Ph]),
2a, 3a-3c, 13i-13j [M(L13).nH2O]), bi-negative tridentate (8a ([UO2(L8)3H2O])), monobasic
hexadentate () chelates, neutral bidentate or bi-negative pentadentate in 4c.
The number of donor sites increases in case of bis Schiff bases where two azomethine nitrogens
and two phenolic oxygen, two methoxy oxygen or neighboring donor atoms participate in
coordination. Also the attached anions (nitrates, OAc) or solvent molecules like water, MeOH
etc satisfy the unoccupied coordination sites of the metal ions. It leads to the appearance of vast
stereochemistry of the ligand. (1d, 1f, 5a, 6a, 9a, 10a-10b, 12a-12f,)
Usually o-vanillin tridentate ligands can give following geometries. i.e.
distorted trigonal bipyramidal configuration in 1c (Ph2Sn[3-(OMe)-2-OC6H3CH=N–

N=C(O)Ph]), 2a ([Sn(C6H5)2(C15H11ClN2O3)]) (with oxygen atoms in axial positions and carbon
& nitrogen atoms in equatorial positions-2a).
Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in 1d

([Mo(NO)2(L1H)2]), 3a ([Ru(L3)(CO)(PPh3)2]), 3b ([Ru(L3)(CO)(PPh3)(py)]), 3c ([Ru(L3)(CO)
(PPh3)(pip)]), 4a (Cr(HL4)Cl2(H2O)](H2O)), 4b (Fe(HL4)2Cl(H2O)](3H2O)), 4c
([Cu(H2L4)2Cl2]·(2H2O)), 13i ([M(L13).nH2O]),
Pseudo-square pyramidal coordination in 1g ([C2H8NO][VO2(C15H12N2O3)]), (The cis-

dioxovanadium(V) moiety adopts pseudo-square pyramidal coordination with the vanadyl
oxygen atom at the apical position, the phenolate, the enolate oxygen atoms, another vanadyl
oxygen atom and the imine nitrogen atom in the basal plane-1g),
Tetrahedral geometry in 4c ([Cu2(L2)Cl2 (H2O)]·(2H2O)), 13j ([M(L13).nH2O])
In the complex molecule, 12a (C24H36O8N4P2S2Cu), two chelating ligands (12) surround the Cu
atom in a trans planar arrangement, so the copper ion is tetra coordinatively bound to two imine
10
nitrogen atoms and two hydroxybenzene oxygen atoms from the two ligands. The geometry
around copper is described as a parallelogram. The structure of the complex resembles a
windmill with the two methoxy groups bonding to benzene rings on either side of the large
common plane and phosphatidyl groups swept to the upper side and the underside of the plane.
The compound Ni[(C2H5O)2PSNHNCPh(o-O)OMe]2 (5a) crystallizes in monoclinic system,

space group P21/n in which Ni ion has slightly distorted trans square planar configuration with
two centrosymmetric molecules of 5. The two phenyl rings and the phosphorylhydrazine
moieties are in one plane forming an extensive delocalized system.
A triclinic P1ˉ space group geometry is observed in compound 1f ([Dy(L1)(NO3)2(DMF)2]). The

DyIII ion of the mononuclear complex (1f) adopts a nine-coordinate distorted pentagonal
interpenetrating tetrahedral geometry; where one ligand, two nitrate and two coordinated DMF
solvent molecules occupy the coordination sites. Four oxygen atoms from two nitrate groups
form a distorted tetrahedron which interpenetrates the distorted pentagonal plane formed by
nitrogen and oxygen of the ligand and oxygen from the DMF molecules. The polydentate Schiff
base ligand coordinates to the Dy centre via two oxygen atoms and one nitrogen atom.
Calix[4]arenes, containing three-dimensional cavities, are popular building blocks in

supramolecular chemistry, especially in molecular recognition. Their controlled synthetic
functionalization allows the use of these compounds in supramolecular chemistry as molecular
scaffolds for the construction of various receptors. Modified calix[4]arene derivatives, having
additional binding sites at the lower rim, enhance the binding ability of the parent calix[4]arene.
A series of pendant Schiff-base calix[4]arene derivatives was synthesized by Mary F. Mahon et
al., in 2008. From which o-vanillin Schiff-base calix[4]arene is our concern. (11) They observed
that the pendant arms did not adopt a face-to-face conformation but instead were bent away from
each other. These conformations were brought about by steric constrictions, as well as the
formation of additional intramolecular interactions between hydroxyl groups on the pendant
arms and an aromatic ring of the calix[4]arene.
11
Similarly, crown ethers are of great interest in the area of molecular recognition. Crown ethers
containing hydrophobic exteriors are lipophilic hosts, which can include cations, especially alkali
(Na in 10a) and alkaline earth metal ions, into their cavities via an ion dipole interaction. Crown
ethers containing Schiff base compounds are known to bind cations in the crown ether cavity in
addition to the coordination of a transition metal center through the NO donor atoms (10b-10c).
1.2. Mode of Coordination of di- or polynuclear Ligands :-
The o-vanillin based tetradentate ligands (6, ) can coordinate to the metal center via imino
nitrogen, deprotonated hydroxyl / phenolic oxygen, vanillic methoxide oxygen, deprotonated
enolic hydroxyl or carbonyl oxygen or carboxylic acid oxygen in neighborhood. It results in the
synthesis of multinuclear metal clusters.
Che-Jung Kuo et al., and Hongshan Ke et al., in 2015, synthesized centrosymmetric dinuclear
([Dy2(HL6)2(NO3)4]·THF·MeCN) & [Dy2(H3L6)2(PhCOO)4]·4H2O (6a) and nonanuclear
compound ([Dy9(μ3-O)4-(μ-OH)6(L62-)4(NO3)4(DMF)4](OH)·H2O·THF·DMF) with triclinic P1ˉ &
monoclinic P21/c space group and monoclinic C2/C space group geometries respectively by
using ligand 6.
Both DyIII ions (in compound 6a) are nine coordinate and the remaining four coordination sites
of each lanthanide / Dy ion are filled by two nitrate or four benzoate anions. Lattice water
molecules also exist in few cases. The Dy centers are in a distorted pentagonal, interpenetrating
tetrahedral arrangement of two nitrates. Charge balance considerations for the molecule indicate
that the ligand must have one negative charge resulting from the ligand being in the keto-form,
and one deprotonated O2 atom. The coordinated water molecule act as intermediate connectors of
hydrogen bonding join the ligands from two adjacent metal / Dy 2 molecules to generate a 1D
supramolecular chain. 6a gives a tricapped trigonal prism configuration
The structure is composed of nine Dy III ions, in which all Dy atoms are eight coordinate and the
rest of the coordination sites are filled by four DMF and four nitrite molecules. The nonanuclear
12
complex can be viewed as two pentanuclear fragments. The metal skeleton can be regarded as
four Dy triangles fused in a vertex-sharing fashion. The Dy 1 adopts a distorted square antiprism
geometry, while the coordination environments of Dy 2, Dy3 and Dy4 centres are distorted
dodecahedra and Dy5 centres are distorted square antiprisms (6d).
The centrosymmetric complex 7a has a nearly linear Dy4 core. Dy1, Dy2 & Dy4 are bridged by
two oxygen atoms each from the ligand (bidentate sites). While Dy3 is bridged by two oxygen
and a nitrogen atom from the ligand (tridentate site). Yun-Nan Guo et al., in 2010, reported that
7a crystallizes as [Dy4(L7)4(MeOH)6] ·2MeOH, in which Dy1 and Dy2 are bridged by three
oxygen atoms from the ligand. The central Dy ions of the Dy4 core are connected by two O
units. The coordination spheres of the dysprosium ions are completed by methanol ligands,
generating eight-coordinate centers with a distorted bicapped trigonal-prismatic geometry and
nine-coordinate with a nearly perfect monocapped square-antiprismatic environment. Strong
inter- and intramolecular hydrogenbonding interactions produce a two-dimensional
supramolecular plane with a zigzag arrangement of the molecules
Po-Heng Lin et al., in 2012, isolated a dimerised form of compound 1 via condensation reaction
of terephthalohydrazide and o-vanillin (9), which further gave a dinuclear centrosymmetric
complex with triclinic P1ˉ space group geometry with DyIII (9a, [Dy2(L9)(NO3)4(DMF)4]·DMF).
This complex could be described as two mononuclear units bridged by the phenyl ring of the
ligand. Each DyIII centre in 9a exhibits a similar coordination environment to complex 1f with
the same atom labels.
1.3. IR Data :-
In free ligand (1-6, 8, 10-13) (1,2, 3, 4, 5, 6, 8, 10, 11, 12, 13, ) a characteristic broad band for
OH group was observed at 3269, 3446, 3371, 3060, 3242, 3200, 3288, 3350, 3060, 3300, 3200
(3060-3446) cm-1. The OH group of the ligands was absent in the complexes (1f, 2a, 3a-3c, 4a-
4c, 5a, 6a-6b, 8a, 10a-10c, 11a, 12a-12f, 13a-13f, 13i-13j, 13k) due to the deprotonation of the
13
ligand. This shows that the phenolic oxygen is coordinated to the metals like Sn, Mo, Dy, V, Zn,
Ru, Cr, Fe, Cu, Ni, U, Rh after deprotonation.
However, the OH group was still present in the complexes (1d, 5a) with range 3370-3445
indicating that the phenolic oxygen of ligand is not involved in coordination with the metals like
Ni.
Another interesting example is the appearance of OH band at 3472, 3430, 3210-3400, 1620,
1630-1640, 940-950, 730-750 in complexes (4a-4c, 8a, 6a, 13a-13f, 13i, 13j, ), it is due to the
stretching, wagging, rocking or deformation modes of the solvents –OH like MeOH, water or –
OH of hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (1, 2, 3, 4, 6, 8,
11, 12, 13) is found to be at 1608, 1606, 1619, 1605, 1685, 1570, 1598, 1606, 1610, 1565 cm -1. It
is shifted to higher frequency (1615, 1640, 1570, 1619-1623, 1597-1666, 1585-1595 cm -1) in all
the complexes spectra (1f, 2a, 4a-4b, 5a, 8a, 10a-10c, 11a, 12a-12f, 13k, 13a-13f, ) indicating
that azomethine nitrogen is involved in the coordination with metals like Zn, Sn, Cr, Fe, Ln
series.
But shifting of this frequency to a lower value in complexes i.e. 1612, 1648, 1615, 1597-1603,
15400-1550 indicates that azomethine nitrogen is involved in the coordination with metals like
Ru (3a-3c, 6a-6b, 4c, 13i, 13j, ) . This lower shift could be attributed to a weakening of the C=N
bonds on adduct formation and this can be explained by the donation of electrons from nitrogen
to the empty d-orbitals of the transition metal ions.
The presence of an amido carbonyl (-C=O) of benzohydrazides in neighborhood shifts its

stretching band either towards higher frequency from 1660 , 1708, 1667 to 16670, 1640, 1602
cm-1 for compounds 1c, 1e, 1g, 4a-4c, 6a-6b, 13k. Or these bands disappear in the complexes
indicating the destruction of the carbony1 moiety due to enolization and consequent proton
replacement with the metal (1a, 1b, 1d, 2a, 3a-3c, 4c, 8a, 13a-13f). Sometimes lower frequency
was observed i.e. from 1580-1590 to 1560-1575 in 13i, 13j.
14
The ν(N-N) stretching vibration in ligand (1,8, 13) is 991, cm-1, 1148, 900-1000, 1055, 1075.
This is also shifted to higher frequency which is 1009 - 1020 cm -1, 1609-1625 cm-1, 1580-1618,
1068, compared to the free ligand further supporting that azomethine nitrogen is coordinated to
metals like Sn, Ni, Zn, U, (1a-1g, 6a-6b, 8a ) . In some cases shifted to lower frequency i.e. 960-
1030 in 13a-13f,
The –OH and –NH stretching vibrations for the phenolic–OH and –NH groups appear as a strong
envelope in the range 3338 –3004 cm-1 (1). Sometimes no envelop occurs and –NH gives peak at
3274-3316, 3135, 3316, 3040, 3410, 3240, cm-1 like in compounds 4, 5, 8, 10, 12, 13.
The N-H peak didn’t disappear even after complexation indicating that the compound retained its
keto form e.g. in compounds 1c, 1e-1g, 5a, 6a-6b, 9a, 12a-12f, 13k, 13i, 13j,
1
1.4. H NMR
Singlet for vanillic -OH proton is found at 12.03, 12.20, 10.7-10.9, 10.85, 10.23, 11.42, 8.33,
11.8 ppm in ligand (1, 2, 3, 4, 6, 8, 10, 11, 12, 13).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (1a-1g, 2a,
3a-3c, 4a-4c, 6a-6b, 8a, 10a-10c, 11a, 12a-12f, 13a-13k) indicated that the phenolic oxygen is
coordinated to the metals like Sn, Mo, Zn, Dy, V, Ru, Cr, Fe, Ni, Mn, Co, Cu, Zn, after
deprotonation.
However, the OH proton signal is still present, with little lower shifts, in few complexes (4d, 5a,)
due to the non-participation of vanillic-OH and less Lewis acidic character. Therefore, the
phenolic oxygen is not coordinated to the central metal ion in the complexes.
Or it may be due to the presence of solvent molecules attached i.e. like MeOH in complex ( 4a-
4c, 6a, 13a-13j) gives a singlet at 4.13, 4.8 ppm
The NH resonance signal for ligand (1, 2, 3, 4, 8, 13) is 11.01, 10.80, 10.8-12.6, 10.9-10.7, 9.30,
10.86 ppm in hydrazine or benzohydrazides. In complexes (1c, 1e-1g, 4a-4c, 13i, 13j) shifted to
15
the upfield region (9.86 - 9.95 ppm) compared to the free ligands, indicating that the
complexation of C=N-NH nitrogen atom to the metal. In few cases, the signal disappeared due to
enolization of carbony1 moiety and consequent proton replacement with the metal (1a, 1b, 1d,
2a, 3a-3c, 8a, ).
Usually the resonance at ~8.6 ppm shifts to 8.5 ppm as –CHO transforms into –CH=N–. The
most important azomethine (-HC=N) resonance signal is found at 8.66, 8.94, 8.8-9.0, 8.42, 9-8.8,
8.17, 8.75, 8.2, 8.27 ppm for ligands (1, 2, 3, 4, 6, 8, 10, 11, 12, 13). After complexation, the
HC=N resonance signal is shifted slightly downfield to 8.29, 8.75, 8.80, 9.72 ppm in all the
complexes (1a-1g, 2a, 3a-3c, 4a-4c. 8a, 10a-10c, 11a, 12a-12f, 13a-13j) indicating that the
azomethine nitrogen is coordinated to the metal ion.
1.5. Applications :-
Hydrazones/ aroylhydrazones which contain the group –CONHN-CH-, are used in analytical
chemistry as selective metal extracting agents (compound 4 to extract Cu-4c), determining metal
ions as fluorimetric / florescent reagents (1f, 13k).
Spectrofluorimetric determination of rhodium(III) was reported by Ning Zhang et al., in 2007, in

the β-CD-rhodium-KBrO3–OVSH catalytic kinetic reaction system (13k).
Various results suggested that the complexes (4a-4b) can act as semiconductors and lie in the
same range of highly efficient photovoltaic materials. 6a behaves as a single molecule magnet
(SMM) with an energy barrier of 42.7 K and a pre-exponential factor (τ0) of 1.31×10-7 s. While
for 7a, the SMM behavior with high anisotropic barrier of 173 K was calculated.
The simple dinuclear systems (6a, ) with facile control of the intradimer magnetic interactions
provide ideal models to map the synergic effect between single-ion anisotropy and magnetic
interactions in enhancing the anisotropic barrier.
Single-Ion Magnet behavior with relaxation barriers (an anisotropic energy barrier) of Ueff = 34
and 42 K were confirmed for 1f and 9a, respectively.
16
Bo Tang et al., in 2003, studied the fluorescent β-cyclodextrin-o-vanillin benzoylhydrazone with
Zn2+ (1f- β-CDP-OVBH-Zn2+). The β-cyclodextrin cavity protected the single state molecule of
the formative fluorescent complex from the quenching of water and soluble oxygen and
improved the quanta yield. The maximum excitation and emission wavelengths were 396 and
486 nm, respectively. This method was successfully applied to the determination of trace
amounts of Zn2+ in tea and human hairs [5].
The compound 11 is found to be the best fluorescent sensor.
Compounds 13i-13j have magnetic properties with Ueff = 2.58 BM and Ueff = 2.01 BM
respectively at 300 K.
Hydrazone complexes are found to possess properties like pesticides, etc (5a).
2- Hydrazinopyridine / isonicotinohydrazide / pyridine carbohydrazone /

picolinohydrazide
Aroylhydrazones entailing o-vanillin can be involved in keto-enol tautomeric interconversion

(Figure-2) Tautomeric equilibrium can also involve aldehyde moiety if the hydroxyl group is
situated in ortho position with respect to the C=N double bond (Structure-C) The tautomeric
interconversion, i.e. isomerization of hydrazones due to solvent effect, pH value or UV
irradiation can also occur (Structures A-C)
Different tautomeric and isomeric forms have different spectral properties and can be
distinguished according to their IR, UV–Vis and NMR spectra. Since A-C isomers can have
diverse chelating properties as well as pharmacodynamics activities, the study of such an
equilibrium is relevant not only from the theoretical point of view, but for further development of
aroylhydrazones as potential drug candidates.
17
Tautomeric interconversion (A-C) is possible and can facilitate complexation with that of metal
cations. But A & B can easily form chelates. As a consequence, aroylhydrazones act as doubly
deprotonated, tridentate O,N,O donors in B .
In HNMR spectra of compounds in DMSO strong deshielding of hydroxyl protons (δ≈12.2 ppm)
due to intramolecular hydrogen bonds was recorded. The signals at 10.79–11.14 ppm assigned to
NH protons indicate hydrogen bond formation between solvent molecules and the amide proton.
That bond was stronger in acetone, causing a downfield shift of the -NH signals to 11.43 ppm. In
chloroform, the signal of amide proton appeared at 9.54 ppm since there is no possibility of H-
bond formation. In methanol, signals of both acidic -OH and -NH protons were missing,
confirming the proposed assignment. The signal of azomethine protons of A and B at ≈8.66 ppm
in DMSO confirmed the two tautomeric configurations of aroylhydrazones. The signal was
missing in C.
Furthermore, the addition of protic polar solvents like water can cause the ketoamine–enolimine
tautomeric interconversion from form A-C, which is usually accompanied by the appearance of a
new band in the spectral region around 400 nm.
in pure, DMSO hydrazones exist as E isomers in ketoamine form with respect to the hydrazide
part, and enolimine with respect to the aldehyde part of the molecules. Preference of the obtained
form is attributed to the p–p conjugation between p-electrons of the C=N bond and the lone
electron pair of the nitrogen of the C=N-N group. Also water had been considered responsible
for tautomerism as well as for isomerism of the structurally related compounds. While increasing
the water content, obtained spectral changes implied hydrogen bonding of aroylhydrazones
through the amide and hydroxyl groups with water molecules. It is very likely that formed
intermolecular hydrogen bonds additionally contributed to the stability of the ketoamine form.
(A) The same structural form revealed in diluted and nearly saturated solutions indicated that
concentration of the hydrazones did not affect equilibria in solution.
The base strength will influence the keto-enol tautomerism and deprotonation of the ligand,
resulting in distinct coordination modes to dysprosium-(III) centers. (18a-18c) (18a-EtN3, 18b-
pyridine, 18c-NaN3). Such a geometry may be a suitable and robust ligand field for slow
18
magnetic relaxation on dysprosium(III) ions. Second, the relative positioning of the different
strong oxygen and nitrogen donor atoms might influence the emergence of magnetic anisotropy.
Keto-A Enol-B Keto-C

R=N
Figure-2: Possible tautomeric forms of aroylhydrazones and E/Z configuration with respect to
the C=N double bond
deprotonated hydroxyl / phenolic oxygen and deprotonated enolic hydroxyl or carbonyl oxygen
or pyridyl nitrogen in neighborhood. It results in the formation of either monobasic bidentate
(16c [Mo(NO)2(HL16)2] , monobasic tridentate 14d [SnCl3(C13H12N3O2)], 14e
[nBuSnCl2(C13H12N3O2)] or dibasic tridentate 15a [(C4H9)2Sn(C14H11N3O3)], 15b
[(C6H5)2Sn(C14H11N3O3)], 15f ([Cu(L15)]2), 15g ([Ni(L15)]2), 15h ([Zn(H2L15)2](NO3)2), 16e
[(C8H17)2Sn(C14H11N3O3)], monobasic hexadentate () chelates, bi-negative tridentate (16i
[UO2(L16)2H2O]),
Various neutral bidentate examples are 14a [Me2SnCl2(C13H13N3O2)], 14b

[Ph2SnCl2(C13H13N3O2)], 14c [nBu2SnCl2(C13H13N3O2)] in which ligand coordinates to the metal
atoms like tin(IV) via azomethine nitrogen and pyridyl nitrogen atoms.
19
stereochemistry of the ligand (14g, 15c-15e, 15f-15h, 16a, 16c, 16i, 16j, 16k, 16l, )
Usually o-vanillin tridentate ligands can give following geometries. i.e. a distorted trigonal
bipyramidal configuration (five-coordinated) can be observed in 15a, 15b, 16d
[(CH3)2Sn(C14H11N3O3)], 16f [(C4H9)2Sn(C14H11N3O3)], 16g [(C6H5)2Sn(C14H11N3O3)], where two
oxygen atoms occupying the axial positions and two carbon atoms and one nitrogen atom (in
same plane) occupy the equatorial positions.
A tetrahedral configuration can be observed in 16m [Mn(L16).H2O], 16n [Ni(L16).H2O], 16o

[Pd(L16).H2O]. While square planner configuration is exhibited by 16p [Co(L16).H2O], 16q
[Cu(L16).H2O], 16r [Zn(L16).H2O].
A monoclinic or orthorhombic space groups (16a-16b) or Octahedral or distorted octahedral

confugration is observed in 16c.
In 16j [Mn(H2L16)2(MeOH)2Cl2], one MnII located on an inversion center with two ligands (16) is
coordinated by its pyridine group. In addition, two Cl atoms and two MeOH molecules fill the
remaining octahedral coordination sphere of the metal center. In the coordination pocket, an
intramolecular H-bond between O-H…..N is present instead of the expected chelated metal
center.
In the Compound 16h ([(CH3)3Sn(C14H12N3O3)]6), the enolization does not occur for the Schiff
base ligand, six trimethyltin(IV) coordination units are linked by the a phenol hydroxyl oxygen
atom from one ligand and pyridinyl N atom from second ligand, this Sn-N weak interaction
forms a 72-membered crown-like macrocycle. Here tin is five-coordinated, with distorted
trigonal bipyramidal geometry in which the apical position is occupied by the oxygen atom and
the nitrogen atom.
20
The tridentate Schiff base ligand (15) coordinate to tin center forms a C=N-N=C conjugated
system, which is introduced into the inner coordination sphere. So the complexes 15c
[(C4H9)6Sn3(C14H11N3O3)2Cl2], 15d [(CH3)6Sn(C14H11N3O3)2Cl2], 15e
[(C6H5)6Sn3(C14H11N3O3)2Cl2], show a centrosymmetric trinuclear structure, in which the central
Sn atom adopts six-coordinated geometry and the other Sn atom adopts five-coordinated
geometry. These interactions contribute to the crystal stability and compactness. The five-
coordinate tin atom exhibits distorted trigonal bipyramidal geometry, surrounded axially by two
oxygen atoms from the Schiff base ligand and equatorially by one nitrogen atom, two carbon
atoms from the alkyl group. So these two carbon atoms and one nitrogen atom are almost in the
same plane. The central six-coordinate tin atom renders with a square pyramidal geometry, in
which two nitrogen atoms occupying the axial positions and two carbon atoms and two chlorine
atom occupying the equatorial positions. So the two equatorial carbon atoms and one nitrogen
atom are almost in the same plane.
To synthesize dinuclear systems and induce significant properties like magnetic anisotropy for
SMMs (single-molecule magnets), specific type of linear, rigid ligands are used. (15,16) Such a
linear ligand provides O,N,O,O based multichelating sites in which the metal centers are bridged
by the phenoxide oxygen and imino nitrogen of single or two ligands. Sometimes vanillic
methoxy oxygen also contributes in coordination. It results in M-O-M mode of attachments (M =
3d, 4f metal ions), (15f-15h, 16a, 16b, ). The remaining coordination sites of the metal ions are
filled by N or O atoms of various pyridine systems or attached groups of ligand, neighboring
complex, attached nitrate anions or solvent molecules like methanol etc.
Po-Heng Lin et al., in 2008, proved that, 16a crystallizes in two different forms i.e.
[Dy2(L16)2(NO3)2(MeOH)2] with monoclinic P21/c and [Dy2(L16)2(NO3)2(MeOH)2] ͚ . MeCN
(2MeCN)] with orthorhombic Pbca space group geometries.
Complex 16k ([Mn2(L16)2(OMe)2] ͚ .2MeCN·2OEt2) crystallizes in the tetragonal space group

I41/a with the asymmetric unit containing half of a dinuclear Mn III unit, one MeCN and one OEt 2
molecule. The complex consists of a dinuclear core, in which two Mn III ions are bound in the
coordination pockets of two ligands and are bridged by two methoxide anions. The two oxygen
21
and a nitrogen atom from the ligands, as well as the oxygen atom of a bridging methoxide anion,
coordinate to MnIII in the equatorial plane. The axial coordination sites are occupied by a
methoxide oxygen atom and a pyridine nitrogen atom. Bond valence sum calculations confirm
the +3 oxidation state of the metal centers.
Complex 16l ([Mn2Mn(L16)2(OMe)2Cl2] ͚ ·MeOH) crystallises in the triclinic P1- space group. It
is a trinuclear complex composed of two Mn III ions and one MnII ion, linked into a one-
dimensional chain. The MnII ion sits on an inversion center which links two terminal Mn III sites
using the methoxide and chloride bridging ligands producing the linear trinuclear complex. Due
to the J–T distortion, the MnIII sites are axially elongated along the Mn–Cl and Mn–CH 3OH
bonds. Bond valence sum calculations and charge consideration confirm the +3 oxidation state of
one Mn and the +2 oxidation state of second Mn. In addition to two -Cl and two -OMe ligands,
the MnII ion is coordinated by two pyridine nitrogen atoms from the neighbouring trinuclear
complexes so these complexes form 1-D polymeric chains in the crystal structure. Two methanol
molecules coordinated to the MnIII ions occupy the space between these chains.
Haiquan Tian et al., in 2013, reported pentanuclear complexes with triclinic P1ˉ space group
geometry in 17a-17b [Dy5(µ3-OH)3(L17)6(H2O)3].3MeOH.9H2O and in 17c [Dy5(µ3-OH)3(HL17)2-
(L17)4(MeOH)(H2O)2].(ClO4)2.6MeOH.4H2O. A total of six polydentate acylhydrazone ligands
wrap around the Dy5 core. In addition, four flexible coordination modes can be observed in their
doubly deprotonated forms. The coordination spheres of the dysprosium ions are completed by
water molecules and MeOH molecules around various Dy atoms, thus generating distorted
dodecahedral, distorted mono-capped square-antiprismatic, and distorted triple capped prismatic.
While two of the ligands have undergone keto–enol tautomerism in case of 17c.
The atmospheric CO2 can be readily trapped as carbonate in a basic medium. The assembly of
ligand 17 with dysprosium salt produces a novel quadruple -CO 32- bridged octanuclear cluster.
Compound 17d ([Dy8(µ4-CO3)4(L17)8-(H2O)8].10MeOH.2H2O) crystallizes in the monoclinic
space group C2/c and contains an octanuclear [Dy8(µ3-CO3)4]16+ core which can be described as a
square anti-prism of Dy centers. Four -CO 32- connects the top and bottom of the square anti-
prism. The metal ions are further linked via bridging carboxy oxygen atoms of eight hydrazone
22
ligands that wrap around the exterior to similar silver twigs binding a nest together. The
coordination geometries of the DyIII ions are either distorted dodecahedral or distorted
monocapped square-antiprismatic. A total of eight water molecules successively occupy the
remaining coordination sites of eight Dy III ions. Additionally ten non-coordinated methanol
molecules and two water molecules of crystallization are located in the crystal lattice. Finally,
weak intermolecular hydrogen-bonging interactions produce a one-dimensional zigzag chain of
the molecules.
A dinuclear trans-dysprosium(III) complex 18a ([Dy2(L18)2(NO3)2(H2O)2].2H2O) crystallizes in

the triclinic space group P1-. Two ligands (18) coordinate two dysprosium centers in an
antiparallel or “head-to-tail” fashion with the tridentate unit (O,N & O from vanillin) and the
bidentate picolinoyl group . Carbonyl oxygen atoms of the ligands bind in their conjugate
deprotonated enol form, and bridge the two metal centers, giving rise to a four-membered Dy 2O2
rhomb, which exhibits a center of symmetry. In addition, one nitrate and one water molecule are
coordinating to each dysprosium ion, leading to a coordination number of 8, which exhibits a
hula-hoop-like geometry whose cyclic ring (hula hoop) is shaped by the stereochemical
preferences of two ligands. The coordinated water molecule binds to the neighboring nitrate via
an intramolecular hydrogen bond. Every Dy2 molecule connects to six lattice water molecules;
meanwhile, each lattice water acts as a hydrogen-bonding connector, joining three Dy2 units.
Compound 18b ([Dy2(HL18)( L18)-(NO3)2(H2O)4].NO3.2CH3OH.3H2O) crystallizes in the space

group P212121, with Z = 4. The molecule occupies a general site, in which two ligands ( 18)
coordinate two dysprosium centers in a parallel fashion, leading to a noncentrosymmetric. One
of the ligands has undergone keto-enol tautomerism. Therefore, in the dideprotonated ligand,
alkoxido atom bridges the two metal centers, the mono deprotonated ligand coordinates two
dysprosium centers with the tridentate unit (O, N and O) and the bidentate o-vanillin group (O
and O), in which the aroylhydrazone part keeps the original keto state. The coordination spheres
of Dy atoms are each completed by two water molecules and one nitrate ligand, making them
nine-coordinate with a monocapped square antiprismatic geometry.
23
Compound 18c (Na[Dy2-(H L18)2(μ2-OH)(OH)(H2O)5].3Cl.3H2O) crystallizes in the space group
P1-, with Z = 2. Evidently, in the presence of a weak base (N 3-), both of the aroylhydrazone
ligands remained in the keto form. Two ligands (18) coordinate Dy1 and Dy2 centers in an
antiparallel fashion with their tridentate unit and bidentate o-vanillin group. complex 3 exhibits a
Dy2(μ-O)3 core, which is created by the phenoxido groups of two ligands and one additional μ 2-
hydroxido group. The coordination spheres of both the Dy atoms are completed by five water
molecules and one ligand, making them nine-coordinate with a distorted monocapped square-
anti-prismatic geometry. Along with coordination on Dy1, and two oxygen, also bridge Na ions
below and above the Dy2 molecule.
Complex 18d exist in two forms. First is [Cu2L18(C5H7O2)(H2O)2]ClO4, second is

[Cu4(L18)2(C5H7O2)2(C5H5N)2](ClO4)2.
The first form consists of one binuclear [Cu2L18(acac)(H2O)2]+ cation and one ClO4- anion. The
two copper centers in the title complex molecule are in different coordination environments. First
Cu atom has a distorted square-pyramidal geometry with the basal plane defined by the N and N
atoms from the pentadentate ligand (18), and O and O atoms from the acac - group. The O atom
from a coordinated water molecule occupies the apical site with a long Cu. Second Cu atom is
coordinated by the O, N and O atoms of the ligand (L 18) and a coordinated water molecule O
atom, forming a square plane. There are three kinds of hydrogen bonds in this complex. first, O–
H(H2O)…….O(H2O) between the coordination water molecules; second, O–H(H2O……
O(phenolic) between the coordination water molecules and phenolic oxygen atoms; third, O–
H(H2O)…..O(ClO4_) between the coordination water molecules and the perchlorate oxygen
atoms. The first two kinds of hydrogen bonds link two adjacent binuclear complex cations into
an extended tetranuclear Cu4 unit with a crystallographic centrosymmetry. Each extended
tetranuclear Cu4 unit connects four neighboring ClO 4_ anions by hydrogen bonds. Each ClO4_
anion links two neighboring tetranuclear Cu4 units through hydrogen bonds.
There is one tetranuclear [Cu4(L)2(acac)2(py)2]2+ cation and two ClO4_ anions in second form of
complex 18d. A diazine N–N group of the pentadentate ligand bridges the two Cu atoms to form
a Cu2 pair. Two Cu2 pairs are connected by two phenolic oxygen atoms of two ligands to get a
centrosymmetrically tetranuclear [Cu4(L)2(acac)2(py)2]2+ cation. The first Cu atom is in a
24
distorted square-pyramidal geometry, which is completed by N, N, O, O in the basal plane and O
in the axial position. The second Cu atom has a distorted square-planar geometry, formed by O,
O, N and N. The aromatic ring and pyridine ring in a ligand are slightly twisted with a dihedral
angle.
2.3. IR Data :-
In free ligand (14, 15, 16, 17, 18) a characteristic broad band for OH group was observed at
3446, 3260, 3250, 3260, cm-1. The OH group of the ligands was absent in the complexes (15a-
15h, 14d-14e, 16a, 16b, 16d-16h, 16i, 16k-16r, 17a-17d, 18a-18d) due to the deprotonation of
the ligand. This shows that the phenolic oxygen is coordinated to the metals like U, Sn, Mo, Dy,
V, Zn, Ru, Cr, Fe, Ni after deprotonation.
However, the OH group was still present in the complexes (14a-14c, 16c, 16j, ) with range 3370-
3445 indicating that the phenolic oxygen of ligand is not involved in coordination with the
metals like Ni.
Another interesting example is the appearance of OH band at 3400, 1600, 970 in complexes (16i,
16k-16r, 18a-18d), it is due to the stretching, rocking or deformation modes of the solvents –OH
like MeOH, water or –OH of hydrated metal ion attached.
envelope in the range ?? cm-1 (). Sometimes no envelop occurs and –NH gives peaks at 3191,
3454, 3000, 3304, 3433, 3273 cm-1 like in compounds 14, 15, 16, 17, 18. The N-H peak didn’t
disappear even after complexation indicating that the compound retained its keto form e.g. in
compounds. (16a, 16b, 16h, 16j-16l, 17c-17d, 18b-18c). But disappearance of the peak confirms
that enolisation occurs that destroy its keto form. i.e. in complexes 15a-15h, 16i, 16c-16g, 16m-
16r, 17a-17b, 18a, 18d.
25
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (14, 16, 17, 18) is
found to be at 1603, 1606, 1608, 1630, 1590, 1608cm -1. It is shifted to higher frequency (1632,
1591-1610cm-1) in all the complexes spectra (14a-14e, 15a-15h, 16i, 16d-16h, 16j-16l, 17a-
17d, 18a-18d) indicating that azomethine nitrogen is involved in the coordination with metals
like Zn, Sn, Cr, Fe, U.
But shifting of this frequency to a lower value in complexes i.e. 16m-16r indicates that
azomethine nitrogen is involved in the coordination. This lower shift could be attributed to a
weakening of the C=N bonds on adduct formation and this can be explained by the donation of
electrons from nitrogen to the empty d-orbitals of the transition metal ions.
Shifting of azomethine frequency from () to higher / lower frequency () in ?? indicates non-

participation of nitrogen in coordination.

stretching band either towards higher frequency from 1695, 1689, 1695, 1650-1700 cm-1 for
compounds 16a, 16b, 16h, 16j-16l, 17c-17d, 18b-18c. Or these bands disappear in the
complexes indicating the destruction of the carbony1 moiety due to enolization and consequent
proton replacement with the metal (15a-15h, 16c-16g, 16i, 16m-16r, 17a-17b, 18a, 18d).
The ν(N-N) stretching vibration in ligand (14, 16) is 991, 1000, cm-1,. This is also shifted to
higher frequency which is 1009-1020, 1010, 1510-1550 cm -1, compared to the free ligand further
supporting that azomethine nitrogen is coordinated to metals like Sn, Ni, Zn, U, (14a-14e, 16i,
16m-16r) .
The infrared spectrum of the free ligand (14,16, ) showed band at 728, 1570 cm-1 which is
assigned to the pyridine or ν(pyridine in plane). This band is shifted to the higher frequencies at
729-739 cm-1 in all the complexes (14a-14e, 16i)
26
2.4. 1HNMR Data :-
Singlet for vanillic -OH proton is found at 10.89, 12.27, 12.2, 12.27 ppm in ligand (14, 15, 16,
17, 18).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (14d-14e,
15a-15h, 16i, 16d-16h, 16a, 16b, 16k-16r, 17a-17d, 18a-18d) indicated that the phenolic
oxygen is coordinated to the metals like Sn, Mo, Zn, Dy, V, Ru, Cr, Fe, U, after deprotonation.
However, the OH proton signal is still present, with little lower shifts, in few complexes (14a-
14c, 16c, 16j,) due to the non-participation of vanillic-OH and less Lewis acidic character. For
this reason, the diorganotin(IV) chlorides are less reactive compare to the monoorganotin(IV)
chlorides. Therefore, the phenolic oxygen is not coordinated to the central metal ion in the
complexes.
Or it may be due to the presence of solvent molecules attached i.e. like MeOH in complex ()
gives a singlet at ppm
The NH resonance signal for ligand (14, 15, 16, 17, 18) is 9.98, 10.71, 11.08, 11.17, 10.71 ppm
in hydrazine or benzohydrazides. In complexes (14a-14e, 16a, 16b, 16h, 16j-16l, 17c-17d, 18b-
18c) shifted to the upfield region (9.86-9.95 ppm) compared to the free ligands, indicating that
the complexation of C=N-NH nitrogen atom to the metal. In few cases, the signal disappeared
due to enolization of carbony1 moiety and consequent proton replacement with the metal (16i,
15a-15h, 16c-16g, 16m-16r, 17a-17b, 18a, 18d).
most important azomethine (-HC=N) resonance signal is found at 8.29, 8.71 8.62, 8.34 ppm for
ligands (14, 15, 16, 17, 18). After complexation, the HC=N resonance signal is shifted slightly
downfield to 8.29-8.47, 9.30, 8.70-8.90 ppm in all the complexes (14a-14e, 15a-15h, 16a-16c,
16i, 16d-16g, 16k-16r, 17a-17d, 18a-18d) indicating that the azomethine nitrogen is coordinated
to the metal ion.
27
The signal at ppm is assigned to azomethine (HC=N) proton in ligand () which is shifted slightly
down field (ppm) in the spectra of complexes () indicating the nonparticipation of this group in
coordination to metal atom
The pyridine-H6 proton signal is shifted to downfield at 8.14 - 8.42, 12.48ppm in all the
complexes (14a-14e,15c-15e, 16h, 16j, ) compared to the free ligands (14, 15, 16, ) (8.11-8.12)
indicating that the pyridyl ring nitrogen atom is also coordinated to the metal
Various compounds are used in analytical chemistry as selective metal extracting agents () as
well as in spectrophotometric determination of certain metal ions (15 for Cu), spectrofluorimetric
determination of Al (15).
A rare dinuclear dysprosium(III) SMMs with remarkably large energy barriers were synthesized
(16a-16b) with relaxation time τ0 = 3 × 10–7 s & 7 × 10–8, while the energy barriers were Ueff / kB
= 56 K & 71 K.
16l exhibits SMM behavior at low temperature with energy barrier of 8.1K.
Two pentanuclear dysprosium(III) SMMs with remarkably large energy barriers were
synthesized (17a-17b) with relaxation regimes of τ0 = 1.7 × 10–5 s with energy barriers 8.1K &
9.7 × 10–8, 37.9 K & 71 K. While 17c exhibited anisotropic barriers of 197 K.
17d shows SMM behaviour with a hysteresis loop at 1.9 K by using a traditional SQUID
magnetometer and an anisotropic barrier Ueff = 74.2 K and a quantum regime of relaxation below
8 K.
T values at 300 K are 27.3, 28.1, and 27.4 cm 3 K mol

χM
-1
for 18a-18c. τ0 = 5.3 × 10–7 s with
energy barriers 69K.
An antiferromagnetic interaction was observed in di- and tetranuclear complex (18d) by

Dan Wang et al., in 2007.
28
Hydrazone complexes are found to possess antimicrobial (), anti-tubercular (16), anti-convulsant
() and anti-inflammatory activities (), insecticidal activities to parasites, fly, beetle, ladybug, and
underground pest, etc (). Moreover, some hydrazone analogues have been investigated as
potential oral iron chelating drugs for the treatment of genetic disorders such as thalassemia ()
and have also been suggested as possible metal chelating agents for treating neurodegenerative
disorders such as Alzheimer disease ().Significant antiproliferative effects in cultured tumor cells
(16f, 16g)
3- Pyridines / Pyrimidines Systems
In non-polar and aprotic solvents all Schiff bases appeared predominantly in the enolimine form.
A shift to the ketoamine tautomer was observed only for compound 20 in polar protic solvents,
deprotonated hydroxyl / phenolic oxygen and pyridyl nitrogen or carbonyl oxygen in
neighborhood. It results in the formation of either monobasic bidentate 20a (Cu(C14H13N2O2)2) ,
23a ([Cu(L23)2(H2O)2]), 23b ([Ni(L23)2(H2O)2]), 23c ([Zn(L23)2(H2O)2]), 23d ([Co(L23)2(H2O)2]),
23e ([UO2(L23)2]), monobasic tridentate 19a (Pd(L19)OAc), 19b (Pd(L19)2) or dibasic tridentate
22a (Cu(L22)X), 22b (Cu(L22)2X), bi-negative tridentate (), monobasic hexadentate () chelates,
neutral bidentate or bi-negative pentadentate in. ()
stereochemistry of the ligand (19b, 21c, 22a, 23a-23e). Sometimes only two phenolic oxygen
29
from bis Schiff bases participate in coordination 26a [(Cl)2La(L26)(H2O)4], 26b [(Cl)2Ce(L26)
(H2O)4], 26c [(Cl)2Nd(L26)(H2O)4], 26d [(Cl)2Sm(L26)(H2O)4], 26e [(Cl)2Gd(L26)(H2O)4], 26f
[(Cl)2Y(L26)(H2O)4].
distorted trigonal bipyramidal configuration in
Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in 23b

[Ni(L23)2(H2O)2], 23d [Co(L23)2(H2O)2], 24a [Cu.L24.(H2O)2],
Pseudo-square pyramidal coordination in
Tetrahedral geometry in 24b [Co.L24.(H2O)2], 25a [(n-But)2Sn(L25)2], 25b [(n-Oct)2Sn(L25)2]
A square planner geometry in 19a (Pd(L19)(OAc)), and 19b (Pd(L19)2) with four coordinating
sites comprised of an N,N,O-tridentate ligand (19) and an acetate ligands.
3.3. IR Data :-
In free ligand (23, 24, 25, 26) a characteristic broad band for OH group was observed at 3385,
3332, 3455, 3425 cm-1. The OH group of the ligands was absent in the complexes (23a-23e, 24a-
24b, 25a-25b, 26a-26f) due to the deprotonation of the ligand. This shows that the phenolic
oxygen is coordinated to the metals like Cu, Ni, Co, Zn, U, Snafter deprotonation.
However, the OH group was still present in the complexes () with range 3370-3445 indicating
that the phenolic oxygen of ligand is not involved in coordination with the metals like Ni.
30
Another interesting example is the appearance of various -OH band (two bands) at 3400-3550,
3332-3407, 3412-3420 & 1605-1660, 738.5, 791.5 in complexes (23a-23d, 24a-24b, 26a-26f), it
is due to the stretching, wagging, rocking or deformation modes of the solvents –OH like MeOH,
water or –OH of hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (20, 23, 24, 25,
26) is found to be at 1625, 1610, 1662.4, 1658, 1650 cm -1. It is shifted to higher frequency (1615,
1640, 1570, 1619-1623, 1597-1666, 1585-1595 cm-1) in all the complexes spectra ( ) indicating
that azomethine nitrogen is involved in the coordination with metals like Zn, Sn, Cr, Fe, Ln
series.
But shifting of this frequency to a lower value in complexes i.e. 1608, 1580-1590, 1660, 1661.5,
indicates that azomethine nitrogen is involved in the coordination with metals like Cu, Ni, Zn,
Co, U, (20a, 23a-23e, 24a-24b). This lower shift could be attributed to a weakening of the C=N
bonds on adduct formation and this can be explained by the donation of electrons from nitrogen
to the empty d-orbitals of the transition metal ions.
But shifting of this frequency to a lower value in complexes i.e. 1625-1638, 1590-1630 indicates
that azomethine nitrogen is not involved in the coordination with metals like Sn (25a-25b, 26a-
26f).
The presence of an amido carbonyl (-C=O) of benzohydrazides / in neighborhood shifts its

stretching band either towards higher frequency from 1701, 1250 cm-1 in 25, 26 to 1712-1716,
1270-1277 cm-1 for complexes 25a-25b, 26a-26f. Or these bands disappear in the complexes
indicating the destruction of the carbony1 moiety due to enolization and consequent proton
replacement with the metal (). Sometimes lower frequency was observed i.e. from 1580-1590 to
1560-1575 in.
The ν(N-N) stretching vibration in ligand () is 991, cm -1, 1148, 900-1000, 1055, 1075. This is
also shifted to higher frequency which is 1009 - 1020 cm-1, 1609-1625 cm-1, 1580-1618, 1068,
31
compared to the free ligand further supporting that azomethine nitrogen is coordinated to metals
like Sn, Ni, Zn, U, ( ) . In some cases shifted to lower frequency i.e. 960-1030 in
envelope in the range 3338 –3004 cm-1 (). Sometimes no envelop occurs and –NH gives peak at
3274-3316, 3135, 3316, 3040, 3410, 3240, cm-1 like in compounds.
keto form e.g. in compounds,
The –NH stretching vibrations (two peaks) in sulfonamide was found to be at 3350 for ligand 23.
These bands either show upward shift or no change in their position in the complexes indicating
the reluctance / non-participation of sulfonamide nitrogen towards coordination; 3060-3100 in
23a-23e.
A new peak of ѵas(SO2) at 1340 in ligand 23 was shifted to 1330-1340 in complexes 23a-23e.
While the value for ѵsy(SO2) at 1160 in 23 was shifted to 1145-1150 in complexes 23a-23e.
These bands either show low field shift or no change in their position in the complexes indicating
the reluctance / non-participation of sulfonamide sulfur towards coordination;
Similarly bands for S-N shifted from 970 (23) to 965-975 (23a-23e) and for C-S from 835 (23)
to 830 (23a-23e) indicates non-participation of sulfur in coordination.
1
3.4. H NMR
Singlet for vanillic -OH proton is found at 13.75, 13.42, 12.7, 14, 9.19, 12.25 ppm in ligand (19,
20, 21, 22, 23, 24, 25, 26).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (19a-19b,
20a, 21a-21c, 22a-22b, 23a-23e, 24a-24b, 25a-25b, 26a-26f) indicated that the phenolic oxygen
is coordinated to the metals like Sn, Mo, Zn, Dy, V, Ru, Cr, Fe, Ni, Mn, Co, Cu, Zn, after
deprotonation.
32
However, the OH proton signal is still present, with little lower shifts, in few complexes () due to
the non-participation of vanillic-OH and less Lewis acidic character. Therefore, the phenolic
oxygen is not coordinated to the central metal ion in the complexes.
Or it may be due to the presence of solvent molecules attached i.e. like MeOH, H 2O in complex
(23a-23d, 24a-24b, 26a-26f) gives a singlet at 4.13, 4.8, 2.22, 3.54, (10.3, 11.1 also in 24a-24b)
ppm
The NH resonance signal for ligand () is 11.01, 10.80, 10.8-12.6, 10.9-10.7, 9.30, 10.86 ppm in
hydrazine or benzohydrazides. In complexes () shifted to the upfield region (9.86 - 9.95 ppm)
compared to the free ligands, indicating that the complexation of C=N-NH nitrogen atom to the
metal. In few cases, the signal disappeared due to enolization of carbony1 moiety and consequent
proton replacement with the metal ( ).
most important azomethine (-HC=N) resonance signal is found at 8.06, 8.75, 8.96, 9.3, 8.76, 8.47
ppm for ligands (19, 20, 21, 22, 23, 24, 25, 26). After complexation, the HC=N resonance signal
is shifted slightly downfield to 8.52, 9.4, 9.9, 8.74, 8.79, 9.90 ppm in all the complexes (19a-19b,
20a, 21a-21c, 22a-22b, 23a-23e, 24a-24b, 25a-25b, 26a-26f) indicating that the azomethine
nitrogen is coordinated to the metal ion.
chemistry as selective metal extracting agents (compound to extract ) as well as in spectroscopic
determination of certain transition metal ions (), determining metal ions as fluorimetric /
florescent reagents ().
A highly sensitive spectrometric and spectrofluorimetric determination of Cu(II) can be done by

precursor 20.
33
Sensors comprising Schiff Base as electroactive ingredient have been reported to exhibit
excellent selectivity for ions like Cu2+. Schiff Bases upon deprotonation form complexes with
Cu2+, which act as charge carriers in the membrane matrix.
The mono- and bis-Schiff bases of o-vanillin and 2,3-diaminopyridine (22) have been used as
ionophores in in PVC membrane as CuII selective electrochemical sensor (22a-22b). These Cu2+
selective sensors were used for the determination of Cu 2+ in the presence of foreign ions both by
direct potentiometry and titration.
Siddappa A. Patil et al., in 2009, proved complex 19a-19b, 21a, 21c as an efficient catalyst
precursor for Suzuki–Miyaura cross-coupling reactions of various aryl bromides with
arylboronic acid.
Various results suggested that the complexes () can act as semiconductors and lie in the same
range of highly efficient photovoltaic materials. behaves as a single molecule magnet (SMM)
with an energy barrier of 42.7 K and a pre-exponential factor (τ0) of 1.31×10-7 s. While for , the
SMM behavior with high anisotropic barrier of 173 K was calculated.
Various complexes are found to be diamagnetic in nature like 23c, 23e, 26a, 26b, 26f.
The simple dinuclear systems (, ) with facile control of the intradimer magnetic interactions
and 42 K were confirmed for and , respectively.
The compound is found to be the best fluorescent sensor.
34
Compounds have magnetic properties with Ueff = 1.59 & 7.54 BM for 26d, 26e.
At 298K the magnetic moment of the complex 21b was 1.58µB.
Hydrazone complexes are found to possess antimicrobial (), antibacterial (24a-24b), anti-
tubercular (), anti-convulsant () and anti-inflammatory activities (), insecticidal activities to
parasites, fly, beetle, ladybug, and underground pest, etc (). Moreover, some hydrazone
analogues have been investigated as potential oral iron chelating drugs for the treatment of
genetic disorders such as thalassemia () and have also been suggested as possible metal chelating
agents for treating neurodegenerative disorders such as Alzheimer disease ().
4- Imidazole / Benzimidazole / Pyrazoles
deprotonated hydroxyl / phenolic oxygen and deprotonated enolic hydroxyl oxygen or carbonyl
or carboxylic acid oxygen in neighborhood. It results in the formation of either monobasic
bidentate (32a-32f), monobasic tridentate () or dibasic tridentate (), bi-negative tridentate (),
monobasic hexadentate () chelates, neutral bidentate or bi-negative pentadentate in.
stereochemistry of the ligand. (,)
35
Octahedral or distorted octahedral or tetragonally distorted octahedral configuration can be
observed in 27b [CoII(L27)2.5MeCN] & [CoII4(L27 )4(MeO)2]·2(ClO4)], 27c [NiII(L27)2.5MeCN] &
[NiII2(L27 )3(MeOH)·(ClO4).2MeOH], 29a [CoII4(L29 )4(H2O)4], 28a [CoII4(L28 )4(H2O)4], 27d
[CuII4(L27)4(MeO)2·2(ClO4).6MeOH]
A mixed ligand (consisting of ligands 27 & 30) gave distorted octahedral geometry
[(CoIIIL27L30).2MeCN]
Distorted square planer geometry can be observed in 27d [CuII (L27)2.MeCN], 32c
[Ni(L32)2]0.3H2O, 32f [Pd(L32)2]2.5H2O.
Tetrahedral geometry in 32a [[MnL32(NO3)]2], 32b [[CoL32(NO3)]2], 32d [[Cu(L32)2]0.3H2O], 32e

[ZnL32(NO3)].
Compounds 27b [CoII(L27)2.5MeCN], 27c crystallize in the triclinic P1- space group and contain
one molecule in the asymmetric unit. These are Co, Ni monomers each, in which the metal
center has a distorted octahedral geometry, coordinating to two ligand molecules and a total of 6
atoms. Each ligand coordinates to Co or Ni via the phenoxide oxygen atoms, the imine group
nitrogen atoms and the carbonyl group oxygen atoms. Five acetonitrile molecules are also
present in the crystal lattice. Each molecule is isolated within the crystal structure as there are no
hydrogen bonds or other supramolecular interactions formed.
Compounds 27b [CoII4(L27 )4(MeO)2]·2(ClO4)] & 27d [CuII4(L27)4(MeO)2·2(ClO4).6MeOH]

crystallize in the monoclinic P21/c space group. The asymmetric unit contains four metal centers,
four ligand molecules, two bridging methoxides and two perchlorate counter ions. The main core
of the cluster is a deformed cubane-like Co 4O4 consisting of four Co centers, two bridging
methoxido atoms, and two bridging phenoxido atoms. Each of the Co centers coordinates to six
atoms and displays a distorted octahedral geometry. The four organic ligands exhibit two
different coordination modes, two ligands per mode. In the first mode, the phenoxide oxygen
atom and the imine nitrogen atom coordinate to one Co center, while the carbonyl oxygen atom
coordinates to a second Co center. In the second mode, one Co centre is coordinated to the
36
phenoxide oxygen atom, the imine nitrogen atom and the carbonyl oxygen atom, while the
phenoxide atom is further bridging two Co centers and the methyl ether group oxygen atom also
coordinates to the third Co center. No hydrogen bonds or other supramolecular interactions can
be found between the molecules within the crystal structure.
Compound 27d crystallize in the triclinic P1- space group and contain one molecule in the
asymmetric unit. It is a Cu monomer in which the metal center coordinates to two ligand
molecules and a total of 4 atoms, having a distorted square planar geometry. Each ligand
coordinates to Cu via the phenoxide oxygen atoms and the imine group nitrogen atoms. One
acetonitrile molecule is also present in the crystal lattice. Also no hydrogen bonding or other
supramolecular interaction can be found within the crystal structure.
The compound, 31 [C15H13O2N3H2O], is nearly planar, with an intramolecular N….O hydrogen

bond. There is a strong intramolecular O-H…..N hydrogen bond and a weak C-H……N
interaction, together with strong N-H…..O and O-H…..N intermolecular hydrogen bonds. The
dimeric molecular structure and hydrogen-bonded step-chain diagrams of 31a [C16H16O7Cu], 31b
[C16H18O8Cu] & hydrogen bonded zigzag chain diagrams 31c [C18H20N2O5Cu] are also given in
scheme 31. The phenolic oxygen atoms lose their protons and gets coordinated to copper in 31a-
31b.
The compound 31a has distorted square-pyramidal configuration with orthorhombic Pbca space
group configuration. The central copper atom is surrounded by two cis-o-vanillinato ligands and
one water molecule forming a square-pyramidal structure with coordination number of five for
Cu. In the extended structure of 31a, there are weak intermolecular π-π ring and C-H…O
interactions. An intermolecular π-π interaction occurs between the phenyl rings. In addition to
these π-π, π-ring interactions, there are five- and six-membered rings in the dimeric structure.
The molecule of 31b possesses inversion center on Cu atom surrounded by two trans-o-
vanillinato ligands and two water molecules forming an octahedral structure with coordination
number of six. It has monoclinic P21/c space group configuration. The ring is involved in an
37
intermolecular C–H……π interaction. In addition to this π ….ring interactions, there are two
five-membered rings and two six-membered rings in the dimeric structure.
The molecular structure of 31c with orthorhombic Pnma space group configuration is given in
which, the central Cu atom in the compound is five-coordinated by two O atoms and two N
atoms from the Schiff base ligand and one O atom from the water molecule. The coordination
geometry around copper can be described as a near square-pyramidal. There is an overall
‘‘butterfly” shape to the molecule, as evidenced by a dihedral angle. There are also weak
intermolecular π-π, π-ring and C-H….O and O-H….O hydrogen-bond interactions in 31c.
Compound 29a [CoII4(L29 )4(H2O)4] is synthesized using a Co4O4 cubane-like core is formed;
however, a transformation of the ligand has taken place. The CH 3 group of the C atom of the
pyrazolone ring is oxidized to a CH 2OH, as confirmed by X-ray crystallography. Compound has
crystallographically imposed 4- symmetry and crystallizes in the tetragonal I41/a space group and
the asymmetric unit consists of one Co II centre, one L2 ligand and one water molecule. There are
no solvent molecules or counter ions present in the structure. The cubane-like Co 4O4 consists of
the four CoII and four bridging O methoxido atoms of the CH 2OH transformed group. Only one
type of coordination mode is present in the structure, as the ligand coordinates to the metal centre
via the imine nitrogen atom, the phenoxide oxygen atom and the CH 2OH transformed group
oxygen atom. A water molecule also coordinates to each of the cobalt centres, thus fulfilling its
distorted octahedral geometry. The crystal structure is stabilized by a strong O–H⋯O
intermolecular hydrogen bond which involves a water oxygen atom as a donor and the phenoxide
oxygen atom as an acceptor.
Compound 28a [CoII4(L28 )4(H2O)4] has crystallographically imposed 4- symmetry a Co4O4

cubane-like core is formed; however, a different transformation of the ligand is observed. The
methyl group connected to the pyrazolone ring is, in the present case, transformed to a CH(OH)2
group. The compound crystallizes in the tetragonal I41/a space group and the asymmetric unit
38
consists of one Co centre, one ligand 28 and one water molecule. There are no solvent molecules
or counter ions present in the structure. The cubane-like Co 4O4 consists of the four Co centres
and four bridging O atoms; the oxygen atom belongs to the transformed CH(OH)2 group. Only
one type of coordination mode is present in the structure, as the ligand coordinates to the metal
centre via the imine nitrogen atom, the phenoxide oxygen atom and an oxygen atom. A water
molecule also coordinates to each of the cobalt centres to fulfil the distorted octahedral
geometry. The crystal structure of 28a is stabilized by a strong O–H⋯O intermolecular hydrogen
bond, which involves a water oxygen atom as a donor and a carbonyl oxygen atom as an
acceptor. The structure is further stabilized by a strong O–H⋯O intramolecular hydrogen bond
within two ligands, in which an oxygen atom of the transformed group participates as a donor.
A mixed ligand (consisting of ligands 27,30) compound crystallizes in the triclinic P1- space
group and contains two molecules in the asymmetric unit. Unlike the three previous structures,
bond valence sum (BVS) indicates III oxidation state for both Co centres. The ligand undergoes
another oxidation and the methyl group connected to the pyrazolone ring is transformed to a
carboxylate. Each molecule contains a CoIII centre, one ligand 27 and one ligand 30 as well as
two acetonitrile solvent molecules. The Co III centre has a distorted octahedral geometry and is
coordinated to one L27 molecule via the phenoxide oxygen atom, the imine group nitrogen atom
and the carbonyl group oxygen atom as well as one L 30 molecule via the imine nitrogen atom, the
phenoxide oxygen atom and the carboxyl group oxygen atom. Two acetonitrile molecules are
also present in the crystal lattice. There are no hydrogen bonds or other supramolecular
interactions formed between the molecules within the crystal structure.
Compound 27c [NiII2(L27)3(MeOH)·(ClO4).2MeOH], is a Ni dimer, crystallizes in the monoclinic

I2/c space group and contains one molecule in the asymmetric unit. Each nickel center is
coordinated to six atoms and displays a distorted octahedral geometry. There are three ligand
molecules in the structure and each exhibits a different coordination mode. First Ni atom is
coordinated to two ligands, while second Ni atom is coordinated to all three. In detail, Ni 1 is
coordinated to the carbonyl oxygen atom of one ligand and the imine nitrogen atoms as well as
the phenoxide oxygen atoms of two ligand molecules. A terminal methanol solvent molecule
also coordinates to the metal centre through the oxygen atom. Ni 2 is coordinated to phenoxide
39
oxygen atoms from all three ligands, the imine nitrogen atom and the phenoxide oxygen atom of
one ligand, as well as the methyl ether group oxygen atom of a second ligand molecule. Two
perchlorate counter ions are also present in the structure along with two lattice solvent
molecules. The crystal structure of 8 is stabilized by strong O–H⋯O intermolecular hydrogen
bonds, which are formed between either two lattice methanol molecules or one lattice methanol
and a perchlorate anion. Further stabilization occurs with the formation of a strong O–H⋯O
intramolecular hydrogen bond within the ligands.
4.3. IR Data :-
In free ligand (27, 31, 32) a characteristic broad band for OH group was observed at 3060, 3300,
3200, 3440 cm-1. The OH group of the ligands was absent in the complexes (27a, 31c, 32a-32b,
32e) due to the deprotonation of the ligand. This shows that the phenolic oxygen is coordinated
to the metals like Sn, Mo, Dy, V, Zn, Ru, Cr, Fe, Cu, Ni, U, Rh after deprotonation.
Another interesting example is the appearance of OH band at 3112-3642, 3500 in complexes

(31a-31c, 32c, 32d, 32f), it is due to the stretching, wagging, rocking or deformation modes of
the solvents –OH like MeOH, water or –OH of hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (27, 31, 32) is
found to be at 1608, 1606, 1619, 1605, 1685, 1570, 1598, 1606, 1610, 1565, 1614 , 1612 cm -1. It
is shifted to higher frequency (1615, 1640, 1570, 1619-1623, 1597-1666, 1585-1595, 1588-1639
cm-1) in all the complexes spectra (27a, 31c, 32a-32f) indicating that azomethine nitrogen is
involved in the coordination with metals like Zn, Sn, Cr, Fe, Ln series.
40
Ru () . This lower shift could be attributed to a weakening of the C=N bonds on adduct formation
and this can be explained by the donation of electrons from nitrogen to the empty d-orbitals of
the transition metal ions.

stretching band either towards higher frequency from 1610 , 1608 cm-1 for compounds 31. Or
these bands disappear in the complexes indicating the destruction of the carbony1 moiety due to
enolization and consequent proton replacement with the metal (). Sometimes lower frequency
was observed i.e. from 1580-1590 to 1560-1575 in 31a-31b (no value given for 31a-31b).
1
4.4. H NMR
Singlet for vanillic -OH proton is found at 11.8, 11.2, 11.12 ppm in ligand (27, 32).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (27a, 32a-
32f) indicated that the phenolic oxygen is coordinated to the metals like Sn, Mo, Zn, Dy, V, Ru,
Cr, Fe, Ni, Mn, Co, Cu, Zn, after deprotonation.
41
Or it may be due to the presence of solvent molecules attached i.e. like MeOH in complex (32c,
32d, 32f) gives a singlet at 4.13, 4.8 ppm
8.17, 8.75, 8.2, 8.27, 9.92, 9.92 ppm for ligands (27, 32). After complexation, the HC=N
resonance signal is shifted slightly downfield to 9.72, 8.52-8.95 ppm in all the complexes ( 27a,
32a-32f) indicating that the azomethine nitrogen is coordinated to the metal ion.

the β-CD-rhodium-KBrO3–OVSH catalytic kinetic reaction system ().
range of highly efficient photovoltaic materials, behave as a single molecule magnet (SMM)
(27b, 27c). While for , the SMM behavior with high anisotropic barrier of 173 K was calculated.
42
Compound 31 is used as ligands in the field of coordination chemistry; it also shows
photochromism and thermochromism in the solid state. Photochromic compounds are of great
interest for the control and measurement of radiation intensity, optical computers and display
systems.
Compounds have magnetic properties with Ueff = BM at 300 K.
Hydrazone complexes are found to possess antimicrobial (), anti-tubercular (), anti-convulsant ()
and anti-inflammatory activities (), insecticidal activities to parasites, fly, beetle, ladybug, and
disorders such as Alzheimer disease ().
5- Diamines / Polyamines:-
The o-vanillin based dianionic tetradentate ligands (if two o-vanillins are present) can coordinate
to the metal center via two imino nitrogen and two deprotonated hydroxyl oxygen (N2O2 donor
atoms), with various geometries like distorted octahedral coordination i.e. 34a [(n-Bu)2Sn(L34)],
crystallizes in the triclinic P-1 space group, here the ligand occupies the four equatorial positions
43
and the n-butyl groups in the trans axial positions. Few other complexes like 34b, 35a, 35b has
shown six co-ordinated distorted octahedral geometries, 34e [Ru(L34)] has octahedral geometry.
In some cases, the complex exhibits weak fluorescence in comparison to the ligands. Metal ions
may quench the fluorescence emission of some Schiff base ligands containing an aromatic ring
due to metal-centered metal-to-ligand charge transfer / ligand-to-metal charge transfer
(MLCT/LMCT) e.g. 34c.
Decacoordinated (51h)
Five coordinated (35a)
Six coordinated (40a)
bidentate () , monobasic tridentate (83a) or dibasic tridentate (), dibasic tetradentate (34a, 34e,
35c) bi-negative tridentate (), monobasic hexadentate () chelates, neutral bidentate or bi-negative
pentadentate in (), bi-negative tetradentate in (51d)
octadentate N2O6 Schiff base ligand 64
reduced Schiff-base complexes (51b) form structures with V=O···V=O-type interactions
Usually o-vanillin tridentate or tetra dentate or octadentate ligands can give following
geometries. i.e.
distorted trigonal bipyramidal configuration in 67a [ZnL67]
44
Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in 34e, 38a,
(83a) [RuX2(EPh3)(L83)], 52b, 53b, 61, 64a, 69b-69e, 75a,
Pseudo-square pyramidal coordination in 74a
Distorted square planar in 67b [CuL67], 84a, 64b
square planar in 34d, 52a , 53a, 56a-b, 69a,
Dodeca hedron geometry in (51h)
Trigonal pyramidal geometry in (51g)
distorted monocapped octahedron (51f)
Tetrahedral geometry in 43a [(n-But)2Sn.L43], 43b [(n-Oct)2Sn.L43], 56a
The metal complexes CoL2: Co2[(L2)2(H2O)2].4H2O and ZnL2: Zn2[(L2)2(CH3COO)2]

obtained were dinuclear complexes with two metal ions acting as bridges joining the two Schiff
bases together. The results indicated that each L2 moieties acted as a tetradentate ligand in
which both oxygen and nitrogen atoms served as coordination sites for the metal ions.(39)
The complex 85a consists of discrete dinuclear entities.
Usually o-vanillin tridentate or tetra dentate dinclear ligands can give following geometries. i.e.
square-pyramidal geometry in 39a, 39b, 85a [LCo(AcO)2Gd(NO3)2]
two signifcant changes occur in the complex 79 the sharpening of one absorption band at
2399cm−1 indicates that neither coordinated nor associated by hydrogen bond, hydroxy groups
exist in the complex molecule, and the splitting apart of another band from 0519cm into 0528
and 0509cm indicates that the imino group takes part in the coordination with Cu atom.
5.3. IR Data :-
45
In free ligand (43, 34, 35, 52, 53, 56, 60, 64, 69, 75, 77, 80, 83,) a characteristic broad band for
OH group was observed at 2350, 3250-3448, 2800-2900, 3399–3328, 3380-3450, 2950-2880,
3421, 3300-3150, 3417, 3400–3300, 3050-3300, 1379 cm-1. The OH group of the ligands was
absent in the complexes (43a-43b, 34a-34g, 35a-35c, 52a, 53a, 56, 64a-64b, 67a-67b, 75a, 80a,
83a, 86) due to the deprotonation of the ligand. This shows that the phenolic or enolic oxygen is
coordinated to the metals like Sn, Mo, Dy, V, Zn, Ru, Cr, Fe, Cu, Ni, U, Rh, Co, Mn, Sm, Si
after deprotonation.
two significant changes occur in the complex 79 the sharpening of one absorption band at
2399cm−1 indicates that neither coordinated nor associated by hydrogen bond, hydroxy groups
exist in the complex molecule, and the splitting apart of another band from 0519cm into 0528
and 0509cm indicates that the imino group takes part in the coordination with Cu atom.
Another interesting example is the appearance of OH band at 3472, 3114.4, 3430, 3210-3400,
1620, 1630-1640, 940-950, 730-750, 3500, 3400-3500, 3575, 3459, 3410, 3600-3300, in
complexes (35a, 51c, 52b, 53b, 55a-55d, 56a-56c, 70a, 86a, 86f ), it is due to the stretching,
wagging, rocking or deformation modes of the solvents –OH like MeOH, water or –OH of
hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (43, 34, 35, 39, 51
52, 53, 56, 60, 61, 64, 67, 69, 70, 75, 77, 80, 83, 84, 86) is found to be at 1595-1630, 1612-1634,
1617, 1636, 1626–1610, 1610-1630, 1624, 1625-1600, 1633.5, 1620, 1617, 1614, 1193, 1610-
1608, 1620.4, 1635 cm-1.
When adduct formation takes place, the azomethine (-HC=N) stretch shifts towards higher
frequencies. (AA2)
It is shifted to higher frequency (1615, 1640, 1570, 1619-1623, 1597-1666, 1585-1595, 1644.4
cm-1) in all the complexes spectra (70a ) indicating that azomethine nitrogen is involved in the
coordination with metals like Zn, Sn, Cr, Fe, Ln, La series.
46
But shifting of this frequency to a lower value in complexes i.e. 34a-34g, 35a, 35c, 39a, 39b,
51f, 51c, 52a-b, 53a-b, 56a-56c, 64a-64b, 67a-b, 69a-69e, 77a-77f, 80, 83a, 86a-86g, 1612-
1634, 1632, 1600, 1602-1624 , 1648, 1615, 1597-1603, 1540-1550, 1585, 1592, 1624-1528,
1606-1624, 1606–1608 indicates that azomethine nitrogen is involved in the coordination with
metals like Ru, Sn, Zn , Co, Cu, Ni, Mn, Sm, U . This lower shift could be attributed to a
weakening of the C=N bonds on adduct formation and this can be explained by the donation of
electrons from nitrogen to the empty d-orbitals of the transition metal ions.
But shifting of this frequency to a lower value in complexes 43a-43b i.e. 1612-1615, indicates
that azomethine nitrogen is not involved in the coordination with metals like Sn () .

stretching band either towards higher frequency from 1646 cm-1 (43) to 1651-1654 cm-1 for
complexes 43a-43b. Or these bands disappear in the complexes indicating the destruction of the
carbony1 moiety due to enolization and consequent proton replacement with the metal ().
Sometimes lower frequency was observed i.e. from 1580-1590 to 1560-1575 in.
The ν(N-N) stretching vibration in ligand () is 991, cm-1, 1148, 900-1000, 1055, 1075. This is
The –OH and –NH stretching and bending vibrations for the phenolic–OH and –NH groups
appear as a strong envelope in the range 3338 –3004, 3240 and 1595, 3250-3100 and 1550-1560
cm-1 (55a-55d, 61c). Sometimes no envelop occurs and –NH gives peak at 3274-3316, 3135,
3316, 3040, 3410, 3240, cm-1 like in compounds.
the absence of C=O and N–H stretching vibrations in the spectra of the complexes ( 64a, 64b)
confirms the Schiff base condensation
The bands at 1396.2 and 817.4 cm–1 in 70a are assigned to the non-coordinated nitrate group
47
5.4. 1H NMR
Singlet for vanillic -OH proton is found at 13.14, 7.70, 10, 11.40-11.65, 13, 13.61, 14.50 ppm in
ligand (43, 34, 35, 51, 60, 75, 77, 86).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (43a-43b,
34a-34g, 35a-35c, 69a-69e, 75a, 77d, 77f, 86e) indicated that the phenolic or enolic oxygen is
coordinated to the metals like Sn, Mo, Dy, V, Ru, Cr, Fe, Ni, Mn, Co, Cu, Zn, Pd after
deprotonation.
gives a singlet at 4.13, 4.8 ppm
The NH resonance signal for ligand (77) is 5.20, 11.01, 10.80, 10.8-12.6, 10.9-10.7, 9.30, 10.86
ppm in hydrazine or benzohydrazides. In complexes (77d, 77f) shifted to the upfield region
(5.16, 5.18, 9.86 - 9.95 ppm) compared to the free ligands, indicating that the complexation of
C=N-NH nitrogen atom to the metal. In few cases, the signal disappeared due to enolization of
carbony1 moiety and consequent proton replacement with the metal ( ).
most important azomethine (-HC=N) resonance signal is found at 8.09, 8.36, 8.61-8.99, 8.6-8.8,
8.91, 8.1, 8.59, 9.01, ppm for ligands (43, 34, 35, 39, 60, 64, 69, 77). After complexation, the
HC=N resonance signal is shifted slightly downfield to 8.29, 8.33-8.46, 8.3, 8.4, 8.97, 9.24, 8.0
ppm in all the complexes (43a-43b, 34a-34b, 35a, 51g, 64a, 69c, 77d, 77f) indicating that the
In case of tetradentate ligands 34, 35 (where ligand to metal ratio is 2:1), the –CH=N resonance
appears as a singlet at 8.37 also two -OCH 3 proton resonance appears as a singlet at 3.83-3.86,
3.8, 3.87, 4.51 ppm (34a-34b, 34e, 35a, 51g, 60) and signal for methylene and methine protons
48
appear as singlet in 4.40-4.60ppm and 6.40-6.60ppm, 2.44-2.77 (34e, 77d, 77f). It may be
deduced that the ligand moieties lie in plane (symmetrical arrangement) and two hydrocarbon
groups on tin are trans to each other.
florescent reagents/ probes (57a, 59a), photoluminescence (51a), as electroluminescent layers
and emiitters in organic light emitting diodes (34c), (51e) .
The mono- and bis-Schiff bases of o-vanillin and 2,3-diaminopyridine have been used as
ionophores in a Cu(II) selective electrochemical sensor (36a)
49
bidentate ( ) , monobasic tridentate () or dibasic tridentate (35a,), monobasic hexadentate ()
chelates.
The o-vanillin based dianionic tetradentate ligand forms complex 35a, that is six-coordinated in a
somewhat distorted octahedral surrounding with the two phenolate-oxygen and two imine-
nitrogen from the Schiff-base building the equatorial plane and a water and a chloro
/thiocyanate- nitrogen in the axial positions. The neutral mononuclear units are assembled into
centrosymmetric dinuclear motifs through hydrogen bonds between the axially coordinated water
molecule of one iron centre and methoxy-oxygen atoms from the Schiff-base of the adjacent iron
atom.
Complexes 35a-35c, were found to be magnetic in nature due to one unpaired electron and are
consistent with the d9 configuration around Cu(II) ion.
Nuanphun Chantarasiri et al., in 2004, reported Metal-containing polyureas, synthesized by the

reaction of metal complex (42a-42b) and diisocyanates like hexamethylene diisocyanate (HDI)
or 4,4'-diphenylmethane diisocyanate (MDI) i.e. 42c-42f at a mole ratio of 1:1 to avoid
crosslinking of the polymers (scheme-65). Reaction outcomes confirmed that the introduction of
metal complex (particularly contain o-vanillin) into a polymer chain increases thermal stability.
6- Quinoline / Naphthalene:-
50
bidentate () , monobasic tridentate (89) or dibasic tridentate (), bi-negative tridentate (),
monobasic hexadentate () chelates, neutral bidentate or bi-negative pentadentate in.
Complex 88 is a six-coordinate copper(II) coordination entity with formula of [Cu(mqmp)2(ClO4)2] in

which the copper(II) ion is coordinated to an alkoxy oxygen and imino nitrogen of two bidentate mqmp
ligands at the equatorial positions, and to two oxygen atoms of the two perchlorate ions at the axial
positions
Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in
Tetrahedral geometry in

6.3. IR Data :-
In free ligand (87, 89, 90, 92 ) a characteristic broad band for OH group was observed at 3452,
3415, 2698, 3200–3500 3269, 3446, 3371, 3060, 3242, 3200, 3288, 3350, 3060, 3300, 3200 cm -1.
The OH group of the ligands was absent in the complexes (90a-90d, 92a-92d) due to the
51
deprotonation of the ligand. This shows that the phenolic oxygen is coordinated to the metals like
Co, Sn, Mo, Dy, V, Zn, Ru, Cr, Fe, Cu, Ni, U, Rh after deprotonation. ,
Another interesting example is the appearance of OH band at 3400, 3400-3200, 3472, 3430,
3210-3400, 1620, 1630-1640, 940-950, 730-750 in complexes (92a-92d, 94a-94c ), it is due to
the stretching, wagging, rocking or deformation modes of the solvents –OH like MeOH, water or
–OH of hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (87, 88, 89, 90,
91, 92 ) is found to be at 1608, 1609, 1615-1610, 1620, 1614, 1600, 1598, 1606, 1619, 1605,
1685, 1570, 1598, 1606, 1610, 1565 cm-1. It is shifted to higher frequency (1615, 1639-1647,
1640, 1570, 1619-1623, 1597-1666, 1585-1595 cm-1) in all the complexes spectra (87a-87m )
indicating that azomethine nitrogen is involved in the coordination with metals like Zn, Sn, Cr,
Fe, Ln (La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu) series.
But shifting of this frequency to a lower value in complexes (92a-92b, 94a-94c) i.e. 1610–1600,
1612, 1648, 1615, 1597-1603, 15400-1550 indicates that azomethine nitrogen is involved in the
coordination with metals like Ru () . This lower shift could be attributed to a weakening of the
C=N bonds on adduct formation and this can be explained by the donation of electrons from
nitrogen to the empty d-orbitals of the transition metal ions.
A medium intensity band at 1410, 1295– 1290 cm-' is due to the phenolic C-0 stretching
vibration of the Schiff base (87, 92, 94). In the complexes, this band appears in the region 1380–
1370, 1361-1385, 1320 cm-'( 87a-87m, 92a-92d, 94a-94c). The phenolic OH and C-0
stretching vibrations are shifted to lower wave numbers, indicating that the oxygen of the
phenolic OH is also coordinated to the lanthanide ions. 87A-87m
Five absorption bands near 1499, 1300, 1026, 814 and 750 cm-' are assigned to the 11 1; L' z, I'
~, and I: vibrations of the coordinated C2v, nitrate group, respectively. The band splittings for
the bidentate coordination are larger in magitude than those for monodentate coordination. The
52
magnitude of v 4-v I for the bidentate mode is in general more than 180 cm-I . The magnitude of
v q--ll I for [LnL, (NO,)]- (N03)2 is in the range 197-211 cm-l , indicating that the nitrate group
is coordinated in a bidentate fashion. (87)
The intense band at 1291, 1247 cm−1 might be assigned to phenolic(C-O)stretching mode (89,
90)
It is shifted to lower frequency 1236-1231 in complexes 90a-90d
The presence of an amido carbonyl (-C=O) of benzohydrazides or lactone carbonyl, triazine ring
in neighborhood at 1728, 1650 in ligand 92, 94 remains unchanged and confirms its non
involvement in coordination (92a-92b, 94a-94c) or shifts its stretching band either towards
higher frequency from 1660 , 1708, 1667 to 16670, 1640, 1602 cm-1 for compounds . Or these
bands disappear in the complexes indicating the destruction of the carbony1 moiety due to
enolization and consequent proton replacement with the metal (). Sometimes lower frequency
was observed i.e. from 1580-1590 to 1560-1575 in.
Band due to ring NH appear at 2847, 3200 in free ligand (90, 94)
It is shifted to 2947-2934 in complexes 90a-90d
The ν(C=S) at 1251, 1135-1085 and 726cm−1 in the free ligand (89) shifts to higher frequency
upon complexation, due to coordination with nitrogen of azomethine, oxygen of hydroxyl, and
sulfur of thione group for complexes (89)
53
The band at 750-700 is de to C-S in ligand 94
1
6.4. H NMR
Singlet for vanillic -OH proton is found at 10.06, 13.19, 12.03, 12.20, 10.7-10.9, 10.85, 10.23,
11.42, 8.33, 11.8 ppm in ligand (89, 90).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (90b)
indicated that the phenolic oxygen is coordinated to the metals like Sn, Mo, Zn, Dy, V, Ru, Cr,
Fe, Ni, Mn, Co, Cu, Zn, after deprotonation.
The NH resonance signal for ligand (90) is 3.95, 11.01, 10.80, 10.8-12.6, 10.9-10.7, 9.30, 10.86
ppm in hydrazine or benzohydrazides. In complexes () shifted to the upfield region (9.86 - 9.95
ppm) compared to the free ligands, indicating that the complexation of C=N-NH nitrogen atom
to the metal. In few cases, the signal disappeared due to enolization of carbony1 moiety and
consequent proton replacement with the metal (90b). and a new peak appears at 11.12 which
confirms conversion of NH into C=N group in complexes 90b
most important azomethine (-HC=N) resonance signal is found at 9.01, 8.1, 9.14, 8.66, 8.94,
8.8-9.0, 8.42, 9-8.8, 8.17, 8.75, 8.2, 8.27 ppm for ligands (89, 90). After complexation, the
HC=N resonance signal is shifted slightly downfield to 8.29, 8.75, 8.80, 9.72, 7,8-8.0, 9.25 ppm
in all the complexes (90b, 94c)
indicating that the azomethine nitrogen is coordinated to the metal ion.
54
The singlets at δ 8.35 and δ 8.72 ppm are coming from pyrimidine ring (C-H) proton in the
spectrum of the ligand (89) and Cd(II) complex (89e), respectively. The multiplets corresponding
aromatic protons appeared between δ 6.99–7.70 ppm and δ 6.96–7.90 ppm are assigned to
aromatic protons, respectively.26,27 The hydroxyl proton (phenolic OH) disappears in the Cd(II)
complex, indicating that the OH group have been deprotonated and bonded to metal ion.
Signal de to SH appear at 9.5 in 94 and absent in 94c

55
7- Thiosemicarbazones. / Thiophenes / Thiazoles
or carboxylic acid oxygen in neighborhood. The S group of schiffs bases were not coordinated to
the metals and S-S coupling was occurred in complex 100a-100b. It results in the formation of
either monobasic bidentate () , monobasic tridentate () or dibasic tridentate (103, 104), bi-
negative tridentate (), monobasic hexadentate () chelates, neutral bidentate or bi-negative
pentadentate in.
The IR spectra show that, H2L is coordinated to the metal ions in a tetradentate manner with ON
and NO donor sites of the azomethine-N, phenolic-OH, enolic sulphonamide-OH and
thiadiazole-N (99a-99g)
Hexa coordinated (103a)
56
Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in 100a-

100b, 99a-99g, 101a-101d, 102a-102c, 103a, 103b, 103f
Tetrahedral geometry in 95a-95c, 98b-98e
Square planar geometry in 98a, 98f, 104b
7.3. IR Data :-
In free ligand (97, 98, 101, 102, 103, 104, 106 ) a characteristic broad band for OH group was
observed at 3413, 3340, 3262-3420, 3475, 3000, 3253, 3250, 3360, 3269, 3446, 3371, 3060,
3242, 3200, 3288, 3350, 3060, 3300, 3200 cm -1. The OH group of the ligands was absent in the
complexes (95a-95c, 97a-97b, 98a-98f, 101a-101d, 102a-102c, 103a-103d, 104b) due to the
deprotonation of the ligand. This shows that the phenolic oxygen is coordinated to the metals like
Sn, Mo, Dy, V, Zn, Ru, Cr, Fe, Cu, Ni, U, Rh, Mn, Co, Pd after deprotonation.
In complexes 106a-106c it is shifted to higher frequencies 3410-3540
Another interesting example is the appearance of OH band at 3303, 3215- 3250, 780-850, 3387-
3392, 3500, 3425, 3419, 3472, 3430, 3210-3400, 1620, 1630-1640, 940-950, 730-750 in
complexes (97a-97b, 98b-98d, 99a-99g, 101a, 102a-102c, 103e), it is due to the stretching,
57
wagging, rocking or deformation modes of the solvents –OH like MeOH, water or –OH of
hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (95, 97, 98,
99,101, 102, 103, 104, 106, 107) is found to be at 1548, 1619, 1600–1635, 1662, 1576, 1525-
1575, 1580, 1635, 1614–1521, 1614-1629, 1632, 1605, 1649, 1608, 1606, 1619, 1605, 1685,
1570, 1598, 1606, 1610, 1565 cm-1. It is shifted to higher frequency (1639, 1570-1582, 1633,
1625, 1639, 1639–1503, 1631, 1590, 1622, 1640, 1615, 1640, 1570, 1619-1623, 1597-1666,
1585-1595 cm-1) in all the complexes spectra (96a-96g, 98b-98e, 104a, 104b) indicating that
azomethine nitrogen is involved in the coordination with metals like Zn, Sn, Cr, Fe, Ln series.
Bands observed in the region 1550– 1560 cm -1 in the spectra of the complexes (95a-95c) are
assigned to (C=N) vibration. This indicates that the azomethine group is not involved in
coordination to metal in the complexes.(95a-95c)
But shifting of this frequency to a lower value in complexes i.e. 1604, 1580–1615, 1588–1599,
1624-1632, 1520-1553, 1604-1631, 1591-1609, 1594 1612, 1648, 1615, 1597-1603, 15400-
1550 indicates that azomethine nitrogen is involved in the coordination with metals like Ru, Cu,
Ni, Pd (97a, 97b, 99a-99g, 100a-100b, 101a-101d, 102a-102c, 103a, 103b, 106a-106c) . This
lower shift could be attributed to a weakening of the C=N bonds on adduct formation and this
can be explained by the donation of electrons from nitrogen to the empty d-orbitals of the
transition metal ions.
This band is absent in complexes 103f
- The position of bands corresponding to (C=O) and (S=O) vibrations is shifted slightly in the
complexes (95a-95c) as compared with the ligand (95), which again indicates that these groups
do not participate in bonding to metal
ν(V=O) (998-962 cm) (107a)
stretching band either towards higher frequency from 1660, 1689 , 1708, 1667 to 16670, 1640,
1602 cm-1 for compounds (101) . Or these bands disappear in the complexes indicating the
destruction of the carbony1 moiety due to enolization and consequent proton replacement with
the metal (). Sometimes lower frequency was observed i.e. from 1689, 1580-1590 to 1655-
1685, 1560-1575 in. 101a-101d
58
The ν(N-N) stretching vibration in ligand (104) is 991, cm-1, 1148, 900-1000, 1055, 1050, 925-
928, 1075. This is also shifted to higher frequency which is 1009 - 1020 cm -1, 1609-1625, 1625,
1070, 1609, 1615, 1616, 952-965 cm-1, 1580-1618, 1068, compared to the free ligand further
supporting that azomethine nitrogen is coordinated to metals like Sn, Ni, Zn, U, (96d, 96e, 96f,
96g, 104a, 104b ) . In some cases shifted to lower frequency i.e. 960-1030 in
envelope in the range 3338 –3004, 3412 cm-1 (95, 99). Sometimes no envelop occurs and –NH
gives peak at 3274-3316, 3135, 3316, 3040, 3410, 3240, cm-1 like in compounds.
v(S-H) band appear at 2500-2600 in ligand 103 disappear in complexes 103a, 103b
N-H band appear at 3130, 3114-3355 in ligand (101, 104) shifts to 3285-3372, 3140, 3346, 3323,
3337, in complex 96a, 96b, 96c, 101a-101d, 104a..
Band for ClO4 appear at 914-1232 in complexes 106a-106c
Ph band appear at 1450-1600, 1461–1364 , 1457-1605, 1453-1597, 1459-1610, 1494-1613,
1453-1600, 1453-1596 in complexes 96a-96g, 98a-98f
The band at 1095, 1306, 1268-1270, 1253, 1280-1290, 1248, 1260 cm -1 assigned to phenolic
(C-O) stretching vibration in the ligand 95, 101, 103, 104 shows a large shift to a higher
frequency at 1280-1321, 1174-1176, 1046-1100, 1290-1298, 1275-1300 , 1290-1315, 1318-1304
in complexes 95a-95c, 99a-99g, 101a-101d, 102a-102c, 103a-103e, 104b which again indicates
the coordination of the Schiff base to metal through this oxygen or to a lower frequency at 1158-
1173 in complex 103f
A weak band in 2848 cm_1 due to -SH group in the free Schiff base ligand was not observed in the IR
spectra of the nickel and palladinum complexes, revealed that thiolate groups in two moles of Schiff base
were deprotonated and coupled to each other in order to form a -S-S- covalent bond. This coupling can be
seen in the X-ray structure of the nickel complex. Also, in these compounds the common bands at 620
cm_1 and about 734 cm_1 were assigned to the S-S and C-S stretches, respectively 100a-100b
1
7.4. H NMR
59
Singlet for vanillic -OH proton is found at 9.90, 11.45, 11.13, 11.19, 12.82 13.42, 7.1, 12.03,
12.20, 10.7-10.9, 10.85, 10.23, 11.42, 8.33, 11.8 ppm in ligand (95, 97, 98, 99, 100, 101, 103).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (95a-95c,
98e, 99a-99g, 100a-b, 101d, 103e, 103f) indicated that the phenolic oxygen is coordinated to the
metals like Sn, Mo, Zn, Dy, V, Ru, Cr, Fe, Ni, Mn, Co, Cu, Zn, Pd, Cd after deprotonation.
The NH resonance signal for ligand (95, 97, 101) is 3.7, 10.75, 9.932, 11.01, 10.80, 10.8-12.6,
10.9-10.7, 9.30, 10.86 ppm in hydrazine or benzohydrazides. In complexes (95a-95c) slightly
shifted in position, indicating that amide proton is not lost during complexation, in complexes
(97a, 97b, 101d) shifted to the upfield region (9.86 - 9.95, 8.5, 10.91, 12.07 ppm) compared to
the free ligands, indicating that the complexation of C=N-NH nitrogen atom to the metal. In few
cases, the signal disappeared due to enolization of carbony1 moiety and consequent proton
replacement with the metal ( ).
most important azomethine (-HC=N) resonance signal is found at 6.9, 8.52, 8.97, 8.1, 9.93, 8.66,
8.94, 8.8-9.0, 8.42, 9-8.8, 8.17, 8.75, 8.2, 8.27 ppm for ligands (95, 97, 98, 100, 101). After
complexation, the HC=N resonance signal is shifted slightly downfield to 8.60, 8.7, 8.17, 7.1,
9.01, 8.70, 7.2, 8.29, 8.75, 8.80, 9.72 ppm in all the complexes (96a, 97a, 97b, 98e, 100b, 101d,
103e) indicating that the azomethine nitrogen is coordinated to the metal ion.
Signal at 1.557 is attributed to methelene protons of cyclohexane ring in ligand 97. The signal is
shifted to 2.3-1.9, 1.6-2.57 ppm due to the methelene protons of cyclohexane ring for the
complex 97a, 97b
60
The phenyl protons in ligand 98, 101u shows signal at 7.03–7.24, 7.22-7.75 shifts at 7.01–7.10,
7.322-7.921 in complex 98e, 101d
The aromatic protons in the range of δ 7.12 – 8.74 ppm suffer a downfield shift in the
complexes (95a-c) because of deshielding due to drainage of electron density from ring to metal
atom.
The multiplet observed at 6.9-7.2, 6.91–7.01ppm for 1H NMR spectrum of the C-H proton of
the phenyl ring of ligand 97, 98 shifted to 6.6-8.2, 6.3-7.66, 6.63–6.94 in complexes 97a, 97b,
98e may be due to the drifting of ring of electrons towards the metal ion
Signal is observed as a singlet at 4.70, 4.9 ppm in complex (97a, 97b) indicating the presence of
water molecules coordinated to the metal atom
A singlet is observed in the region 3.936, 3.96, 3.74, 3.8, 3.18, 4.00 due to the aromatic –OCH3
protons of phenolic methoxy group of ligand 97, 98, 99, 100, 101, 103 shifts to 3.94, 3.4, 2.96,
3.60 in complex 98e, 100b, 101d, 103e
The multiplets of the aromatic protons in 100a-100b appeared in the range of 6.65–7.23 ppm. On
the other hand, 1H NMR spectrum indicated the aliphatic protons of -S-CH2- as a triplet signal
at 2.49 (100) and 3.04 ppm,(100b) and also exhibited a triplet signal due to -N-CH2- resonances
at 3.74 (100) and 3.85 ppm (100b) which showed a down field shift

61
deprotonated hydroxyl / phenolic oxygen and deprotonated enolic hydroxyl oxygen or
carbonyl or carboxylic acid oxygen in neighborhood. It results in the formation of either
monobasic bidentate ( ) , monobasic tridentate (96a-96c,) or dibasic tridentate (), monobasic
hexadentate (96d-96g) chelates
Usually o-vanillin tridentate ligands can give following geometries. i.e. a distorted trigonal
bipyramidal confugration can be observed in 96d, 96f,. Distorted octahedral confugration is
observed in 96a.
8- Alcohols :-
62
or carboxylic acid oxygen in neighborhood. ligand coordinates to a metal centre with one ethoxy
oxygen atom, one amino nitrogen atom and one phenoxide oxygen atom (108b) It results in the
formation of either monobasic bidentate () , monobasic tridentate () or dibasic tridentate (), bi-
negative tridentate (), monobasic hexadentate () chelates, neutral bidentate or bi-negative
pentadentate in.
distorted square planar in 112a, 114b, 131a
distorted square pyramidal in 115a
the molecular structure of (109c) consists of two Zn(II) ions, two ligands and two acetato
ligands. Therefore, all complexes (109c) are dinuclear species.
63
Metal atom are five coordinate in (109a, 110b ) and six coordinate in (109b )
Usually o-vanillin tridentate or tetra dentate polynuclear ligands can give following geometries.
i.e.
distorted octahedral geometry in (109c, 114c)
tetragonal pyramid (113a)
distorted tetrahedral geometry in 120a
Square pyramidal geometry in 120b
8.3. IR Data :-
In free ligand (116, 117, 118, 119 ,132 ) a characteristic broad band for OH group was observed
at 3454, 3625, 3200-3300, 3040, 3421-3454, 3269, 3446, 3371, 3060, 3242, 3200, 3288, 3350,
3060, 3300, 3200 cm-1. The OH group of the ligands was absent in the complexes (119f-119g)
due to the deprotonation of the ligand. This shows that the phenolic oxygen is coordinated to the
metals like Sn, Mo, Dy, V, Zn, Ru, Cr, Fe, Cu, Ni, U, Rhafter deprotonation.
Very strong bands at 1270 cm–1 were assigned to in-plane bending (O–H) vibration of the
ligands (116). This band is shifted in the complexes (116a-116c) toward lower frequencies as a
result of the coordination of the nitrogen to the metal ion. This feature can be explained to be due
to the withdrawing of electrons from the nitrogen atom to the metal ion as a result of
coordination.
IR spectra of the ligands (116, 117, 118) show a shoulder of a broad band of weak intensity
around 2800–2900, 2700–2980cm–1. This band is ascribed to the O–H stretching vibration,
which is known to shift significantly to lower frequencies because of OH…N intramolecular
hydrogen bonding. (116a-116c) This band disappeared in the complexes (117a-117c, 118a-118c)
because of proton substitution by metal coordination to the oxygen.
64
Another interesting example is the appearance of OH band at 3472, 3350-3423, 3426, 3610-
3620, 3430, 3210-3400, 1620, 1630-1640, 940-950, 730-750 in complexes (117a-c, 118a-c,
119c, 132a-c ), it is due to the stretching, wagging, rocking or deformation modes of the solvents
–OH like MeOH, water or –OH of hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (115, 116, 117,
118, 119) is found to be at 1608, 1606, 1619, 1605, 1685, 1591, 1605–1625, 1617, 1641, 1641–
1639, 1570, 1598, 1606, 1610, 1565 cm-1. It is shifted to higher frequency (1615, 1640, 1620,
1570, 1616, 1619-1623, 1597-1666, 1585-1595 cm-1) in all the complexes spectra (115a, 131a )
indicating that azomethine nitrogen is involved in the coordination with metals like Zn, Sn, Cr,
Fe, Ln series.
But shifting of this frequency to a lower value in complexes (116a-116c, 117a-117c, 118a-118c,
119f-g, 119c) i.e. 1612, 1592-1639, 1606, 1580–1615 ,1606-1619, 1648, 1615, 1597-1603,
Ru, Co, Ni, Cu () . This lower shift could be attributed to a weakening of the C=N bonds on
adduct formation and this can be explained by the donation of electrons from nitrogen to the
empty d-orbitals of the transition metal ions.
The bands at 1494–1501cm-1 were assigned to the diazo group in all the complexes (117a-117c,
118a-118c) and the azo-linked Schiff base ligands (117, 118). The spectra of the complexes did
not show any shift of the frequency of the –N=N– band, which may be explained by non-
participation in complex formation

cm-1 for compounds . Or these bands disappear in the complexes indicating the destruction of the
65
These bands are absent in 115a
The peak at 1633, 1626, 1543, 1541, 1471, 1468, 1638, 1540, 1469 in (109a, 109b. 110a) can be
attributed to stretching vibration of C=C of phenyl ring or imino C=N group
A strong peak at 1170, 1090 should be de to presence of perchlorate anion ClO4- (111ba, 112a)
The IR spectra exhibit strong absorption at 2087 which is due to vibration of N3- anion (109b)
The infrared spectra of Schiff base ligands (117, 118, 119) showed bands around 1250– 1275,
1265, 1195–1265cm-1 assignable to the phenolic C–O vibration. However, in the spectra of the
metal complexes (117a-117c, 118a-118c, 132a-132c), the C–O band shifted to the lower region
1200cm-1. In the complexes (119f-119g) the C-O stretching vibrations appear at a slightly higher
value (1290– 1315 cm-1) showing that coordination also occurs through the phenolic oxygen
atoms.
a strong absorption bands at 3515 cm_1 and 2950 cm_1 which are attributed to the stretching
bands of the free hydroxyl and methylene groups respectively in complex 131a
a band at 1444 cm_1 due to t(C–O) of the phenolic group is observed in complex 131a
1
8.4. H NMR
11.8 ppm in ligand ().
66
The singlet signal of the OH proton on salicylaldeyde ring is observed at 10.32, 10.13 ppm
because of intramolecular hydrogen bonding with the nitrogen atom on the naphthalene ring
(116, 117)
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (119f-119g)
The NH resonance signal for ligand (116, 117, 118,) is 11.01, 11.2, 10.33, 10.52, 10.80, 10.8-
12.6, 10.9-10.7, 9.30, 10.86 ppm in hydrazine or benzohydrazides. In complexes () shifted to the
upfield region (9.86 - 9.95 ppm) compared to the free ligands, indicating that the complexation
of C=N-NH nitrogen atom to the metal. In few cases, the signal disappeared due to enolization of
carbony1 moiety and consequent proton replacement with the metal ( ).
most important azomethine (-HC=N) resonance signal is found at 8.03, 8.37, 8.2–8.7 ,8.22, 8.43,
8.66, 8.94, 8.8-9.0, 8.42, 9-8.8, 8.17, 8.75, 8.2, 8.27 ppm for ligands (116, 117, 118, 132, 119f-
119g). After complexation, the HC=N resonance signal is shifted slightly downfield to 8.29,
8.75, 8.80, 9.72 ppm in all the complexes () indicating that the azomethine nitrogen is
coordinated to the metal ion.
a singlet at 3.78, 3.66, 3.71, 3.95, 3.7-3.9 ppm may be assigned to the protons of the methoxy
group of ligand (116, 117, 118, 119f-119g, 132)
multiplets at 6.84– 7.61, 6.42–7.65, 6.41–7.61, 6.61-7.29, 6.9–7.8 ppm may be assigned to the
aromatic protons of ligand (116, 117, 118, 132, 119f-119g)
67
A new hydrazone peak in the spectrum of ligand 117, 118 was found at the 15.31, 15.80 ppm,
confirming the suggested presence of the keto-hydrazone tautomer
The NMR spectra of the metal complexes (116a-116c, 117a-117c, 118a-118c ) could not be
obtained as all are paramagnetic
florescent reagents, (). photoactive material (113a)

the β-CD-rhodium-KBrO3–OVSH catalytic kinetic reaction system (). And detection of alminim
through easy and fast flow injection system sing the OVAC ligand, (133a)
68
To synthesize dinuclear systems and induce significant properties like magnetic anisotropy for
SMMs (single-molecule magnets), specific type of linear, rigid ligands are used. (108) Such a
linear ligand provides O,N based multichelating sites in which the metal centers are bridged by
the phenoxide oxygen and imino nitrogen of single or two ligands attached. Sometimes vanillic
methoxy oxygen also contributes in coordination. It results in M-O-M mode of attachments (M =
3d, 4f metal ions), (108a, 108c, 108d, ). The remaining coordination sites of the metal ions are
filled by N or O atoms of various pyridine systems or groups in ligand, neighboring complex,
attached nitrate anions or solvent molecules like methanol etc.
In dinuclear systems, all the metal centers show different coordination environments e.g. 108d ,
among three attached dysprosium, Dy1 and Dy3 are eight-coordinate and can be described as
having an approximately square-antiprismatic coordination geometry, and Dy2 is nine-
coordinate with a distorted tricapped trigonal prism geometry.
Also 108a-108d act as SMMs.
9- Diols :-
69
bidentate () , monobasic tridentate () or dibasic tridentate (), bi-negative tridentate (), monobasic
hexadentate () chelates, neutral bidentate or bi-negative pentadentate in.
Complex consists of two doubly bonded oxido groups and a tridentate chelate ligand, which binds
vanadium through the deprotonated phenolato and terminal alkoxido O-atoms, and the imino N-atom
(136a-b)
distorted trigonal bipyramidal configuration in 137c
Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in 137a
Tetrahedral geometry in 138a-138c, 139a-139c
square pyramidal coordination in 135a-b
70
Reactions of MnX2 meltsalt (X=Cl and ClO4) and a quinquedentate Schiff base ligand together
with its coligand azides in MeOH produced the unprecedented assembly of novel octa- and
hexadecanuclear manganese clusters containing two and four alternant tetrahedral MnIII, MnII
cores bridged by Schiff base ligands and versatile azides groups (134b)
The unprecedented deca nuclear complex (142i), is constituted of two sets of m5-CO32- bridged
Nd5 pentagons, held together through acetate and alkoxide bridges of the multidentate Schiff-
base ligand. The most salient feature in the crystal structure of 142i is the occurrence of the
pentanuclear aggregate [Nd5(m5CO3)(OAc)9(HL)(H3L)(CH3OH)], in which the CO32- anion
is trapped in the middle of the pentagon, and binds to five different metal centres with a chelating
and bridging configuration.
The uncoordinated alcohol arm of the central ligand binds to an acetate group via an
intramolecular hydrogen bond (142i)
In the centrosymmetric tetranuclear complex (142a),

[Ni4(C12H15NO3)2(CH3COO)2(N3)2(CH3OH)2].2CH3OH, the asymmetric unit comprises half of a
complex molecule and a methanol solvent molecule. The NiII ions display two different
coordination environments: (i) two O atoms from the Schiff base ligand, two O atoms from
symmetry-related methanol molecules and an O atom from an acetate group, one N atom from
the azide group, and (ii) two O atoms and one N atom from the Schiff base, one O atom from
methanol, one O atom from the acetate anion, and one N atom from the azide group.
Reactions of MnX2 meltsalt (X=Cl and ClO4) and a quinquedentate Schiff base ligand together
with its co-ligand azides in MeOH produced the unprecedented assembly of novel octa- and hexa
deca nuclear manganese clusters containing two and four alternant tetrahedral MnIII-MnII cores
bridged by Schiff base ligands and versatile azides groups (142c, 142g)
In all the complexes (137b) the saccharide moiety adopts a chair conformation and has a β-
anomeric form
pentagonal-bipyramidal 137b
71
9.3. IR Data :-
In free ligand ) a characteristic broad band for OH group was observed at, 3269, 3446, 3371,
3060, 3242, 3200, 3288, 3350, 3060, 3300, 3200 cm -1. The OH group of the ligands was absent
in the complexes () due to the deprotonation of the ligand. This shows that the phenolic oxygen
is coordinated to the metals like Sn, Mo, Dy, V, Zn, Ru, Cr, Fe, Cu, Ni, U, Rhafter
deprotonation.
Another interesting example is the appearance of OH band at 3472, 3365–3442, 3430, 3210-
3400, 1620, 1630-1640, 940-950, 730-750 in complexes (138a-c, 139a-c ), it is due to the
stretching, wagging, rocking or deformation modes of the solvents –OH like MeOH, water or –
OH of hydrated metal ion attached
The infrared spectra of the azo-linked Schiff base ligands 138, 139 displayed a shoulder of a
broad band of weak intensity around 2730–2988 cm)1. This band was ascribed to the O–H
stretching vibration, which is known to shift significantly to lower frequencies because of OH…
N intramolecular hydrogen bonding. This band disappeared in the complexes 138a-c, 139a-c due
to proton substitution by metal coordination to the oxygen
The Infrared spectra of 136a-b show active ν(OH) vibrations at 3352-3413 with the binding of
the imine nitrogen revealed by lowering of the resonance frequency of the ligand 136
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (138, 139) is
found to be at 1608, 1606, 1619, 1605, 1685, 1570 , 1636-1637, 1598, 1606, 1610, 1565 cm-1. It
is shifted to higher frequency (1615, 1640, 1570, 1619-1623, 1597-1666, 1585-1595 cm -1) in all
the complexes spectra ( ) indicating that azomethine nitrogen is involved in the coordination with
metals like Zn, Sn, Cr, Fe, Ln series.
72
But shifting of this frequency to a lower value in complexes i.e. 1620-1629 , 1610-1618, 1612,
1648, 1615, 1597-1603, 15400-1550 indicates that azomethine nitrogen is involved in the
coordination with metals like Ru, V (136a-b, 138a-138c, 139a-139c) . This lower shift could be
attributed to a weakening of the C=N bonds on adduct formation and this can be explained by the
donation of electrons from nitrogen to the empty d-orbitals of the transition metal ions.

The infrared spectra of azo-linked Schiff base ligands 138, 139 showed bands at 1218–1225
cm)1 assignable to the phenolic C–O vibration. However, in the spectra of the metal complexes
138a-138c, 139a-139c, the C–O band shifted to the lower region (1151–1193 cm)1
The bands at 1492–1498 cm)1 were assigned to the stretching vibration of the diazo group of the
ligands (138, 139) The infrared spectra of the complexes 138a-138c, 139a-139c did not show
any frequency shift of the –N=N– band, which may be explained by non-participation in
complex formation.
the antisymmetric stretching vibrations νas(COO–) emerged at 1595 cm-1 for complex 134a,
73
Symmetric stretching vibrations νs(COO–) for the same group appeared at 1442 cm-1 in complex
134a
The characteristic ν(V=O) stretch appears as a medium-strong band at 983 cm-1 for complex
136a-b,
1
9.4. H NMR
Singlet for vanillic -OH proton is found at 12.03, 10.05, 12.20, 10.7-10.9, 10.85, 10.23, 11.42,
8.33, 11.8 ppm in ligand (138).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes () indicated
that the phenolic oxygen is coordinated to the metals like Sn, Mo, Zn, Dy, V, Ru, Cr, Fe, Ni, Mn,
Co, Cu, Zn, after deprotonation.
The broad signals at 10.21 and 12.54 p.p.m. may be considered as azo ring OH and naphtholic
OH protons, respectively. This indicates that very strong hydrogen bonds exist between the diazo
nitrogens and the hydroxyl protons. (138)
74
most important azomethine (-HC=N) resonance signal is found at 8.66, 8.3, 8.40, 8.94, 8.8-9.0,
8.42, 9-8.8, 8.17, 8.75, 8.2, 8.27 ppm for ligands (136, 138, 139). After complexation, the HC=N
resonance signal is shifted slightly downfield to 8.29, 8.75, 8.80, 9.72 ppm in all the complexes
() indicating that the azomethine nitrogen is coordinated to the metal ion.
The resonances between 3.2-3.6 ppm are attributed to the –CH2OH moieties in ligand 136 which
shifts towards 2.9-3.4 ppm in complexes (136a-b)
The resonance at 3.8, 3.62, 3.64 ppm is attributed to the methoxy group –OCH3 of the ligand .
136, 138, 139
the resonance at 3.7 ppm being attributed to the –N-CH moiety in ligand 136
The signals between 6.5-7.1, 6.50–7.81, 6.43–7.76 ppm is attributed to the presence of aromatic
protons in ligand 136, 138, 139 shifts to 6.3-7.1 ppm in complexes (136a-b)

75
The ligands 140, crystallized in the triclinic space group.
The addition of different co-ligands in o-vanillin derived Schiff’s bases (monometallic

coordinated) form ternay complexes and can create interesting variations in coordination sphere,
space configuration and in the electron density distribution around transition metal / simply
metal complexes e.g.o-vanillin based bidentate ligands can coordinate to the metal center via
imino nitrogen and deprotonated hydroxyl oxygen, while various species in neighboring co-
ligands also contribute in coordination to metal center. It results in the formation of either
monobasic bidentate (140a,) , monobasic tridentate (140c-140d) or monobasic tetradentate
(140b) chelates
Presence of 1,10-phenanthroline as co-ligand (140b) exhibits electronic properties and high

cleavage efficiency. Imidazole (10e-10f) or benzimidazole derivatives like 2,4,5-
triphenylimidazole (140c) in histidyl residue of metalloprotein and possess several metal binding
sites while 2-trifluoromethylbenzimidazole (140d) can yield complexes that could serve as
model compounds for purine nucleobases and selectively inhibit endothelial cell growth and
suppress angiogenesis in vitro and in vivo.
76
149b,140c were found to be magnetic in nature.
10- Carboxylates / Amino Acids :-
bidentate () , monobasic tridentate () or dibasic tridentate (), bi-negative tridentate (), monobasic
hexadentate () chelates, neutral bidentate or bi-negative pentadentate in.
77
10.3. IR Data :-
In free ligand ( ) a characteristic broad band for OH group was observed at 3269, 3446, 3371,
3060, 3242, 3200, 3288, 3350, 3060, 3300, 3200 cm -1. The OH group of the ligands was absent
in the complexes () due to the deprotonation of the ligand. This shows that the phenolic oxygen
is coordinated to the metals like Sn, Mo, Dy, V, Zn, Ru, Cr, Fe, Cu, Ni, U, Rhafter
deprotonation.
Another interesting example is the appearance of OH band at 3472, 3430, 3210-3400, 1620,
1630-1640, 940-950, 730-750 in complexes ( ), it is due to the stretching, wagging, rocking or
deformation modes of the solvents –OH like MeOH, water or –OH of hydrated metal ion
attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand () is found to be at
1608, 1606, 1619, 1605, 1685, 1570, 1598, 1606, 1610, 1565 cm -1. It is shifted to higher
frequency (1615, 1640, 1570, 1619-1623, 1597-1666, 1585-1595 cm-1) in all the complexes
spectra ( ) indicating that azomethine nitrogen is involved in the coordination with metals like
Zn, Sn, Cr, Fe, Ln series.
Ru () . This lower shift could be attributed to a weakening of the C=N bonds on adduct formation
and this can be explained by the donation of electrons from nitrogen to the empty d-orbitals of
the transition metal ions.
78
10.4. 1H NMR
11.8 ppm in ligand ().
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes () indicated
that the phenolic oxygen is coordinated to the metals like Sn, Mo, Zn, Dy, V, Ru, Cr, Fe, Ni, Mn,
Co, Cu, Zn, after deprotonation.
79
8.17, 8.75, 8.2, 8.27 ppm for ligands (). After complexation, the HC=N resonance signal is
shifted slightly downfield to 8.29, 8.75, 8.80, 9.72 ppm in all the complexes () indicating that the

80
In case of carboxylates, the extent of separation ∆ (∆ = ѵ as COO- - ѵs COO- ) suggests the binding
mode of carboxylates. i.e. ∆ (monodentate) > ∆ (ionic) > ∆ (bridging bidentate) > ∆ (chelation
bidentate)
Usually ∆ value of ~160-170 cm-1 corresponds to ionic carboxylate group, while the ∆ ~187-200
cm-1 indicates monodentate coordination. Upon complexation, change in the force field around
the metal atom causes redistribution of the electron density which shifts ѵ as (COO-) to higher
wave number with respect to ionic acetates (∆ ~ 170 cm -1) and leads to monodentate coordination
of acetates. However, the shifting of ѵ as (COO-) to lower wavenumbers with respect to the ionic
group leads to bidentate acetates (∆ <170 cm -1). The ѵas (COO-) for ‘bridging’ and ionic acetates
shows slight difference in their frequencies.
Similarly Pyroles (144a, 144b), 2,2'-bipyridine, pyridine etc can………

Adding an amino acid moiety or heterocyclic–amino acid conjugates to o-vanillin to form new
drugs and/or pro-drugs, offer great potential in increasing the solubility of the molecule and
minimizing the toxicity, act as catalytic inhibitors (144, 149-164, 166, 167, 169, 171).
81
bidentate () , monobasic tridentate () or dibasic tridentate (150a, 150b, 151a-155a, ), monobasic
hexadentate () chelates.
In 2006, Guangbin Wang & James C. Chang confirmed through IR data that compounds 150a,
153a, 154a, 155a exhibit square planner (d-d band between 15336 and 15360 in Cu) while 150b,
151a, 152a, 153b, 154b give a tetrahedral geometry (no d-d band because of d 10 electronic
configuration of the Zn2+ ion).
11- Miscellenous :-
deprotonated hydroxyl / phenolic oxygen or methoxy oxygen (in few cases) from o-vanillin and
nitrogen, deprotonated hydroxyl oxygen or carbonyl oxygen in neighborhood. It results in the
formation of either monobasic bidentate 175a ([Cu(L175)2]), 175b ([Ni(L175)2]), 175c ([Zn(L175)2]),
175d ([Co L175]2), 175e (Nd(L175)(NO3)2(H2O)2), 175f (Th(L175)(NO3)3(H2O)2), 175g (UO2(L175)
(OAc)(H2O)), monobasic tridentate () or dibasic tridentate (), bi-negative tridentate (), monobasic
hexadentate () chelates, neutral bidentate or bi-negative pentadentate in. tetracoordinated in
(175a)
stereochemistry of the ligand. (175a-175d,)
82
Tetrahedral geometry in 175b ([Ni(L175)2]), 175d ([Co L175]2)
11.3. IR Data :-
In free ligand (175) a characteristic broad band for OH group was observed at 3380 cm -1. The
OH group of the ligands was absent in the complexes (175a-175g) due to the deprotonation of
the ligand. This shows that the phenolic oxygen is coordinated to the metals like Cu, Ni, Zn, Co,
Nd, Th, U after deprotonation.
Another interesting example is the appearance of OH band at 3400-3550 & 1605-1660 in

complexes (175e-175g), it is due to the stretching, wagging, rocking or deformation modes of the
solvents –OH like MeOH, water or –OH of hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (175) is found to
be at 1615 cm-1.
It is shifted to higher frequency (1615, 1640, 1570, 1619-1623, 1597-1666, 1585-1595 cm -1) in
all the complexes spectra ( ) indicating that azomethine nitrogen is involved in the coordination
with metals like Zn, Sn, Cr, Fe, Ln series.
83
But shifting of this frequency to a lower value in complexes (175a-175g) i.e. 1590-1600
indicates that azomethine nitrogen is involved in the coordination with metals. This lower shift
could be attributed to a weakening of the C=N bonds on adduct formation and this can be
explained by the donation of electrons from nitrogen to the empty d-orbitals of the transition
metal ions.

The –NH stretching vibrations (two peaks) in sulfonamide was found to be at 3320 & 3230 for
ligand 175. These bands either show upward shift or no change in their position in the complexes
indicating the reluctance / non-participation of sulfonamide nitrogen towards coordination; 3300-
3360 & 3200-3260 in 175a-175g.
Sometimes no envelop occurs and –NH gives peak at 3274-3316, 3135, 3316, 3040, 3410, 3240,
cm-1 like in compounds.
A new peak of ѵas(SO2) at 1345 in ligand 175 was shifted to 1330-1340 in complexes 175a-175g.
While the value for ѵsy(SO2) at 1160 in 175 was shifted to 1155-1160 in complexes 175a-175g.
These bands either show low field shift or no change in their position in the complexes indicating
the reluctance / non-participation of sulfonamide sulfur towards coordination;
84
Similarly bands for S-N shifted from 960 (175) to 960-965 (175a-175g) and for C-S from 840
(175) to 840-850 (175a-175g) indicates non-participation of sulfur in coordination.
11.4. 1H NMR
Singlet for vanillic -OH proton is found at 12.06 ppm in ligand (175).
The absence of vanillic OH proton signal in the 1H NMR spectra of the complexes (175a-175g)
Or it may be due to the presence of solvent molecules attached i.e. like MeOH, H 2O in complex
(175e-175g) gives a singlet at 4.13, 4.8 ppm
most important azomethine (-HC=N) resonance signal is found at 8.96 ppm for ligands (175).
After complexation, the HC=N resonance signal is shifted slightly downfield to 8.29, 8.75, 8.80,
9.72 ppm in all the complexes () indicating that the azomethine nitrogen is coordinated to the
metal ion.
In few cases it shifts to little upfield (8.65) indicating the participation of azomethine nitrogen in
coordination. (175a-175g)
85

Compounds 175b, 175f, 175g are found to be diamagnetic in nature.
86
Ligand 180 acts as a bidentate ligand coordinated through phenolic oxygen and azomethine
nitrogen only. The other coordination sites of the metal are occupied by water molecules and
anions (like Cl-) forming [Ln(L180)Cl2.2H2O].
11.3. IR Data :-
In free ligand (180, ) a characteristic broad band for OH group was observed at 3400 vcm -1. The
OH group of the ligands was absent in the complexes (180c-180f) due to the deprotonation of the
ligand. This shows that the phenolic oxygen is coordinated to the metals like La, Ce, Pr, Nd after
deprotonation.
Another interesting example is the appearance of OH band at 3400, 730-740 in complexes (180c-
180f), it is due to the stretching, rocking or deformation modes of the solvents –OH like MeOH,
water or –OH of hydrated metal ion attached
Furthermore, the stretching vibration of azomethine (-HC=N) value for ligand (180) is found to
be at 1600 cm-1. It is shifted to higher frequency (1610-1640 cm-1) in all the complexes spectra
(180c-180f, ) indicating that azomethine nitrogen is involved in the coordination with metals like
La, Ce, Pr, Nd.
But shifting of this frequency to a lower value in complexes i.e. indicates that azomethine
nitrogen is involved in the coordination with metals like Ru () . This lower shift could be
87
attributed to a weakening of the C=N bonds on adduct formation and this can be explained by the
donation of electrons from nitrogen to the empty d-orbitals of the transition metal ions.

stretching band either towards higher frequency from cm-1 for compounds. Or these bands
disappear in the complexes indicating the destruction of the carbony1 moiety due to enolization
and consequent proton replacement with the metal ().
The ν(N-N) stretching vibration in ligand (, ) is. This is also shifted to higher frequency which is,
like Sn, Ni, Zn, U, () .
envelope in the range cm-1 (). Sometimes no envelop occurs and –NH gives peak at cm -1 like in
compounds.
The compound 172a (in 20% aqueous ethanol, K2CO3 as base, 60°C) can catalyze Suzuki-
Miyaura cross coupling reactions of various arylhalides and arylboronic acids. The encapsulated
Pd shows outstanding stability, no significant leaching and reusability at least 5 times without
any significant decrease in activity which make the catalyst cheap and highly desirable to address
the environmental concerns.
The o-vanillin based bidentate ligands can coordinate to the metal center via imino nitrogen,
deprotonated hydroxyl or phenolic oxygen i.e. not deprotonated (lone pairs of oxygen act as
donor sites). It results in the formation of either monobasic bidentate () or neutral bidentates
(173a-173m).
88
In 173a-173m, the complexes are neutral molecules where the central Ln(III) ion is ten-
coordinated in biapical anti-hexahedron prism geometry, in which four oxygen atoms of the
phenolic hydroxy and methoxy groups of two bidentate Schiff base ligands (173) and six oxygen
atoms provided by the three NO3- anions are well coordinated.
173d showed fluorescence quenching phenomena while DNA binding studies.
Shu-Hua Zhang et al., reported a disc-like heptanuclear cluster [Ni7(immp)6(OMe)6] ・ (ClO4)2

(where immp = 2-iminomethyl-6-methoxyphenol) by using microwave assisted solvothermal
method, and confirmed its spin glass nature. The complex crystallizes in trigonal space group P3̅.
Six nitrogen and six phenoxo groups of immp anionic ligand (singly deprotonated to form
phenolate site) bridged six nickel ions on the rim, which are linked to the central nickel ion
through six -OCH3 bridging groups that act as ‘bottom’ to form the disc-like structure. The
coordination geometry of the central Nickel ion is a slightly distorted octahedron. (Scheme-155).
The spin glass nature of compound 179 (scheme-155) with relaxation time τ 0 = 1.28 × 10–15 s and
the energy barrier Ueff / kB = 70.4 K was confirmed by Shu-Hua Zhang et al., in 2015.
89

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Schiff bases form complexes with various metals like Sn, Ni, Zn, Ln etc in both deprotonated

Figure : Co-ordination mode of o-vanillin

polynuclear metal complexes, also known as coordination clusters (CCs),

A large number of chemotherapeutic agents and cytokines (particularly complexes) imply

Table 1: IR data for Metal-Oxygen & Metal-Nitrogen Coordination in Complexes

10a ClO4- 623-1099

Table : Activity Data of Homometallic Complexes

Aroylhydrazones entailing o-vanillin can be involved in keto-enol tautomeric interconversion

1.1. Mode of Coordination of Mononuclear Ligands :-

Usually o-vanillin tridentate ligands can give following geometries. i.e.

distorted trigonal bipyramidal configuration in 1c (Ph2Sn[3-(OMe)-2-OC6H3CH=N–

Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in 1d

Pseudo-square pyramidal coordination in 1g ([C2H8NO][VO2(C15H12N2O3)]), (The cis-

Tetrahedral geometry in 4c ([Cu2(L2)Cl2 (H2O)]·(2H2O)), 13j ([M(L13).nH2O])

The compound Ni[(C2H5O)2PSNHNCPh(o-O)OMe]2 (5a) crystallizes in monoclinic system,

A triclinic P1ˉ space group geometry is observed in compound 1f ([Dy(L1)(NO3)2(DMF)2]). The

Calix[4]arenes, containing three-dimensional cavities, are popular building blocks in

1.2. Mode of Coordination of di- or polynuclear Ligands :-

The presence of an amido carbonyl (-C=O) of benzohydrazides in neighborhood shifts its

Spectrofluorimetric determination of rhodium(III) was reported by Ning Zhang et al., in 2007, in

The compound 11 is found to be the best fluorescent sensor.

2- Hydrazinopyridine / isonicotinohydrazide / pyridine carbohydrazone /

Aroylhydrazones entailing o-vanillin can be involved in keto-enol tautomeric interconversion

Keto-A Enol-B Keto-C

2.1. Mode of Coordination of Mononuclear Ligands :-

Various neutral bidentate examples are 14a [Me2SnCl2(C13H13N3O2)], 14b

A tetrahedral configuration can be observed in 16m [Mn(L16).H2O], 16n [Ni(L16).H2O], 16o

A monoclinic or orthorhombic space groups (16a-16b) or Octahedral or distorted octahedral

2.2. Mode of Coordination of di- or polynuclear Ligands :-

Complex 16k ([Mn2(L16)2(OMe)2] ͚ .2MeCN·2OEt2) crystallizes in the tetragonal space group

A dinuclear trans-dysprosium(III) complex 18a ([Dy2(L18)2(NO3)2(H2O)2].2H2O) crystallizes in

Compound 18b ([Dy2(HL18)( L18)-(NO3)2(H2O)4].NO3.2CH3OH.3H2O) crystallizes in the space

Complex 18d exist in two forms. First is [Cu2L18(C5H7O2)(H2O)2]ClO4, second is

Shifting of azomethine frequency from () to higher / lower frequency () in ?? indicates non-

The presence of an amido carbonyl (-C=O) of benzohydrazides in neighborhood shifts its

T values at 300 K are 27.3, 28.1, and 27.4 cm 3 K mol

An antiferromagnetic interaction was observed in di- and tetranuclear complex (18d) by

3- Pyridines / Pyrimidines Systems

3.1. Mode of Coordination of Mononuclear Ligands :-

Usually o-vanillin tridentate ligands can give following geometries. i.e.

distorted trigonal bipyramidal configuration in

Octahedral or distorted octahedral or tetragonally distorted octahedral configuration in 23b

Pseudo-square pyramidal coordination in

Tetrahedral geometry in 24b [Co.L24.(H2O)2], 25a [(n-But)2Sn(L25)2], 25b [(n-Oct)2Sn(L25)2]

3.2. Mode of Coordination of di- or polynuclear Ligands :-

The presence of an amido carbonyl (-C=O) of benzohydrazides / in neighborhood shifts its

A highly sensitive spectrometric and spectrofluorimetric determination of Cu(II) can be done by

The compound is found to be the best fluorescent sensor.

At 298K the magnetic moment of the complex 21b was 1.58µB.

4- Imidazole / Benzimidazole / Pyrazoles

4.1. Mode of Coordination of Mononuclear Ligands :-

Usually o-vanillin tridentate ligands can give following geometries. i.e.

distorted trigonal bipyramidal configuration in

Pseudo-square pyramidal coordination in

Tetrahedral geometry in 32a [[MnL32(NO3)]2], 32b [[CoL32(NO3)]2], 32d [[Cu(L32)2]0.3H2O], 32e

Compounds 27b [CoII4(L27 )4(MeO)2]·2(ClO4)] & 27d [CuII4(L27)4(MeO)2·2(ClO4).6MeOH]

The compound, 31 [C15H13O2N3H2O], is nearly planar, with an intramolecular N….O hydrogen

4.2. Mode of Coordination of di- or polynuclear Ligands :-

Compound 28a [CoII4(L28 )4(H2O)4] has crystallographically imposed 4- symmetry a Co4O4

Compound 27c [NiII2(L27)3(MeOH)·(ClO4).2MeOH], is a Ni dimer, crystallizes in the monoclinic

Another interesting example is the appearance of OH band at 3112-3642, 3500 in complexes

The presence of an amido carbonyl (-C=O) of benzohydrazides in neighborhood shifts its