Journal Pre-proof

X-ray crystal structure, spectroscopic and DFT computational studies of H-bonded

charge transfer complexes of tris (hydroxymethyl)aminomethane (THAM) with
chloranilic acid (CLA)

Ali El-dissouky, Hemmat A. Elbadawy, Tarek E. Khalil, Doaa Saied El-Sayed, Asmaa
A. Attia, Sabine Foro
PII: S0022-2860(19)31166-4
DOI: https://doi.org/10.1016/j.molstruc.2019.127066
Reference: MOLSTR 127066

To appear in: Journal of Molecular Structure

Received Date: 30 June 2019

Revised Date: 10 September 2019
Accepted Date: 11 September 2019

Please cite this article as: A. El-dissouky, H.A. Elbadawy, T.E. Khalil, D.S. El-Sayed, A.A. Attia, S.
Foro, X-ray crystal structure, spectroscopic and DFT computational studies of H-bonded charge
transfer complexes of tris (hydroxymethyl)aminomethane (THAM) with chloranilic acid (CLA), Journal of
Molecular Structure (2019), doi: https://doi.org/10.1016/j.molstruc.2019.127066.

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 X-ray crystal structure, spectroscopic and DFT computational studies of
H-bonded charge transfer complexes of tris
(hydroxymethyl)aminomethane (THAM) with chloranilic acid (CLA)
Ali El-dissoukya, Hemmat A. Elbadawya,1, Tarek. E. Khalila,2, Doaa Saied El-
Sayeda, Asmaa A. Attiaa and Sabine Forob

a
Chemistry Department, Faculty of Science, Alexandria University, P.O.box 426,
Ibrahimia, Alexandria 21321, Egypt

b
FB Material wissenschaft, FG Strukturforschung, Technische Universitaet
Darmstadt, Alarich-Weiss-Str. 2, D-64287 Darmstadt, Germany

Abstract
The crystal and molecular structures of two new synthesized charge transfer complexes
produced from the reaction of tris(hydroxymethyl)aminomethane, THAM and 2,5-
dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, CLA) in the mole ratios (2:1)
[I] and (1:1) [II], have been studied. The; FT-IR and 1H-NMR spectral data of the
complexes are confirmed by single-crystal X-ray crystallography. The single-crystal X-ray
crystallography, indicated the formation of both inter- and intra-molecular hydrogen
bonding as well as the proton transfer from CLA to THAM. The electronic transition
spectra of these two complexes as acetonitrile (AN), methanol (MeOH), ethanol (EtOH)
solutions are recorded. The molecular compositions of the formed complexes in the three
solvents determined by Job's method, support 1:1 mole ratio complex, whatever the
polarity of the solvent. The high values of charge transfer complex formation constants,
KCT determined by applying the minimum–maximum absorbance method, indicated the
formation of stable CT-complexes, with the order Ethanol > Methanol >> Acetonitrile.
Computational study incorporated the use of TD-DFT with PCM as solvation model are
applied for energy minimization and estimation of the stabilization energy for the produced
complexes. The geometrical parameters (bond lengths and angles) of the formed CT
complexes are computed and analyzed. Furthermore, Mulliken atomic charges, molecular
potential energy surface, HOMO and LUMO molecular orbitals of the formed complexes
are presented. A good agreement between experimental and DFT computational analysis
has been found.

Keywords: Charge transfer, Spectroscopy, Hydrogen bonding, chloranilic, tris

(hydroxymethyl)aminomethane, X-ray, DFT.

2 1 2 2
Corresponding author elbadawy_hm@yahoo.com Corresponding author tarekakel@yahoo.com

1
1. Introduction
The highly applicable, tris(hydroxymethyl)aminomethane, THAM, is a very interesting
compound, which is used as a buffer in the pH range between 7.5 and 8.5, for the treatment
of severe metabolic acidosis in specific circumstances in medicine [1, 2],biochemistry and
molecular biology[3]. It is also used as a primary standard to standardize acid solutions for
chemical analysis and to increase permeability of cell membranes [4].From the chemistry
point of view, it can undergo reactions analogous to primary amines, −NH2 , such as Schiff
base formation. Its Schiff base derivatives have high biological activities including anti-
tumor, antibiotic, anticancer, antihistamine, antifungal, anti-inflammatory and used as
corrosion inhibitor[5] as well as, behaving powerful coordinating ligands towards many
metal ions which are used as catalysts in epoxidation of alkenes and as potential
biomimetic reagents [6, 7]. It was used as a modifier of activated carbon (AC–THAM) and
applied as a solid-phase extracting agent [8]. It can also undergo a non-covalent interaction
through hydrogen bonding, due to the presence of the three CH2OH, which can give more
complex non-covalent associations when it interacted with the acids. However, non-
covalent bonded 3D structures of anhydrous organic salts from tris (hydroxymethyl)
aminomethane and organic acids have been reported[9]. Generally, charge-transfer (CT)
interaction between electron acceptors and various electron donors play an important role
in various physical properties of materials; magnetic, electrical conductivity and optical
properties[10-17]. A great number of charge transfer receptors have been reported under
the basic construction strategy of employing hydrogen bonding[18]. The hydrogen bonds
work as efficient bridges to mediate electron transfer between bonded species and initiate
the so-called proton coupled electron transfer[19, 20]. Generally, CT-interaction between
electron acceptors, such as benzoquinones, and electron donors containing nitrogen, oxygen
or sulfur atoms play an important role in the field of drug-receptors binding mechanism
[21, 22], surface chemistry[23], applications in solar energy storage[24], uses as organic
superconductors[25], and in many biological systems in the field of DNA binding,
antibacterial, antimicrobial, antifungal [26-28], insecticide, antitumor, anti-inflammatory, in
ion transfer through lipophilic membranes and drug receptor binding mechanism[29-35] .
Furthermore, the density functional theory (DFT) and the time-dependent density
functional theory (TD-DFT) have been used as valuable tools to calculate spectroscopic

2
properties of charge transfer and hydrogen bonded complexes [10-16, 35-38]. Moreover,
THAM-chloranilate system was applied, as selective chelating agent, for the determination
of Mg in natural and mineral waters with satisfactory results and recoveries in the range of
97–100%.[39]. But, however, there is no complete information about the charge transfer
complexes of Tris(hydroxymethyl)aminomethane, THAM- chloranilic acid, CLA- couple,
the present study aims to give more information about the chemistry of THAM-chloranilic
acid CT complexes, through synthesis and characterization of two new complexes where
THAM acts as an electron donor and chloranilic acid (CLA) as an electron acceptor using
(1:1) and (2:1) molar ratios, respectively. Also, we will match their X-ray molecular
structures of the prepared complexes with the theoretical studies by the application of DFT
using Lee-Yang-Parr correlation functional (B3LYP) with basis set 6-31G (d,p) [40, 41]
computing the optimized structures, geometrical parameters, reactivity parameters,
Mulliken atomic charges and computing the distribution of electron density on frontier
molecular orbitals of donor, acceptor and the formed complexes, as well as HOMO and
LUMO energies.

2. Experimental
2.1. General

All chemicals used were of analytical grade. Chloranilic acid (2,5-dichloro-3,6-dihydroxy-

1,4- benzoquinone), (CLA) (purity ≥ 98%) was obtained from Sigma-Aldrich. Tris-
hydroxymethylaminomethane, THAM were supplied by Across Organics. Spectroscopic
grade acetonitrile, methanol and ethanol were purchased from Sigma-Aldrich Chemical
Company, Germany and used without further purification. The CHN analysis were obtained
microanalytically at a Perkin-Elmer elemental analyzer (Model 2400II). FT-IR spectra
(KBr disks; three millimeter thickness) were recorded in the 350 – 4000 cm-1 range on a
Perkin-Elmer FT-IR Spectrophotometer-FTIR1650. The 1H-NMR spectra were obtained on
a DELTA2_NMR500 MHz instrument using TMS as an internal reference and d6-DMSO
as the solvent. The electronic absorption spectra of the donor, acceptor and formed charge
transfer (CT) complexes were recorded over the wavelength range of 250 - 700 nm using a
double beam UV-Vis (T80 + UV/Vis) spectrometer, PG Instruments Ltd, UK.

3
2.2. X- Ray crystal and molecular structure

X-ray diffraction data were collected on CrysAlis CCD, Oxford Diffraction limited,
version 1.70.14 (2002), using graphite monochromated MoKα radiation (λ = 0.71013 Å) at
Technische Universitaet Darmstadt, FB Materialwissenschaft, FG Strukturforschung,
Darmstadt, Germany. The structures were solved by direct method with SHELXS–97;
refinement was done by full–matrix least squares on F2 using the SHEXL–97[42].
Hydrogen atoms were positioned with idealized geometry using a riding model and were
refined with isotropic displacement parameter. Drawing of the molecules was produced
with ORTEP3[43]or PLATON [44].

2.3. Synthesis of THAM- CLA complexes:

Ethanolic solutions (25 mL) of CLA (1.045 g, 5 mmol) and THAM (1.211 g, 10 mmol)]in
case of complex I (1:2 mole ratio) and CLA (1.045 g , 5 mmol) and THAM (0.605 g, 5
mmol)] in case of complex II ( 1:1 mole ratio) were mixed and refluxed at 80○C for 2
hours. The solutions were allowed to evaporate slowly at room temperature and the isolated
crystals were filtered off, washed several times with EtOH followed by diethyl ether and
dried over anhydrous CaCl2 in a vacuum desiccator for 24 hrs. The same complexes were
also isolated by using methanol or acetonitrile as solvents. [(CLA)(THAM)2],I, (% yield is
95.5, m.p. is 200 oC and Calcd for C14H24Cl2N2O10 (451.25): C, 37.23; H, 5.32; N, 6.20.
Found: C, 37.20; H, 5.02; N, 6.00) .[(CLA)(THAM)]2.H2O, II,( %yield is 86.0, m.p. is
220oC and Calcd for C20H28Cl4N2O15 (678.24): C, 35.39; H, 4.13; N, 4.13 . Found: C,
35.24; H, 4.32; N, 4.21).

2.4. Preparation of standard solutions of THAM and CLA

Freshly prepared standard stock solutions of both THAM and CLA , 2.0 × 10−3 mol/dm3,
were obtained by dissolving accurate weight in the appropriate volume of solvent.
Solutions for spectroscopic measurements were made by mixing proper volumes of donor
and acceptor stock solutions with the solvent.

4
2.5. Determination of the formation constants of the CT-complex (KCT)

The formation constants (KCT), was determined by applying the minimum–maximum

absorbance method [45] according to the following procedure. One milliliter of CLA stock
solution (2.0 × 10−3 mol/dm3) was transferred into a series of 10 mL calibrated measuring
flasks. To each of these were added different volumes of the freshly prepared stock THAM
solution (2.0 × 10−3 mol/dm3) and diluted to the mark with methanol, ethanol or
acetonitrile. The least concentration of THAM led to the minimum absorbance of the
complex (Amin). The concentration of the electron donor (THAM) is increased gradually
and the absorbance is recorded at the absorption band of the CT-complexes (Amix) until we
got the highest constant absorbance (Amax). The CT-formation constants (KCT) were
estimated using equation (1):

 

 =   (1)




where, Amax is the maximum absorbance of the complex, Amin is the minimum absorbance
of the complex, Amix is absorbance values between Amax and Amin and CTHAM is the
concentration of the added THAM in mol/dm3[45].
3. Results and discussion
3.1. Synthesis and characterization
The reaction between THAM and CLA proceeds with the formation of either a charge
transfer complex with H-bond formation or through the H-bond formation without charge
transfer depending on the molar ratio as shown in Scheme 1. However, the crystal
structures in the solid state can differ greatly from structures in solutions.
O

OH Cl

Cl OH

O
1 molar ratio of THAM 2 molar ratio of THAM

O
OH HO
Cl O
OH OH
NH3 O Cl
OH
HO OH
Cl O NH2
H Cl O H3N
O OH HO
O OH

[1(CLA):1(THAM)] [II] [1(CLA):2(THAM)] [I]

Scheme1 : Proposed structures for complexation between THAM and CLA

5
3.2. Fourier-Transform Infrared spectra (FT-IR)
A comparison for the significant band positions between the donor (THAM), acceptor
(CLA) and the prepared complexes; [I] and [II] show enough insight to the way of complex
formation. The remarkable changes in band intensities and frequencies in the FT-IR spectra
of the complexes compared with reactants (Fig. 1) display the following:
1. The carbonyl ν C=O at 1664 and 1631 cm-1 in (CLA) appeared as only one band at 1601
cm-1 in the two complexes.
2. The ν(C–C1) at(847, 745 cm-1) in CLA are shifted to(834, 724 cm-1) and(837, 722 cm-1) in
the spectra of [I] and [II], respectively.
3. The ν(NH) of the amino group at 3291 and 3190 cm-1 in the spectrum of THAM appeared
as only one band at 3255cm-1 in the two complexes, suggesting the participating of
amino group in hydrogen bonding with the OH group of CLA.
4. The FT-IR spectrum of complex [I] exhibits a broad band characteristic of ν (NH3+) at
3152 cm-1( absent in the spectrum of [II]) suggesting a proton transfer from CLA to the
amino group of THAM. Accordingly, it is concluded that complex I possesses H-
bonding and proton transfer while complex II possesses only a H- bonding.

6
Figure 1. FT-IR spectra of THAM, CLA and complexes [I] and [II] ,in solid state.

3.3. 1H-NMR spectra

The 1H-NMR spectra of the complexes [I] and [II], Fig. 2, show that upon complex
formation, the aliphatic CH2 and the OH protons of THAM exhibit slightly down field shift
, relative to the free base, appearing at δ 3.48- 4.50 (6H) and 7.64 (3H) ppm, respectively,
in the spectrum of complex [II] and at δ 3.48, 4.99 (6H) and 7.79 (3H) in the spectrum of
complex [I]. Another broad signal was found at δ 5.05 ppm in the spectrum of complex [II]
attributable to hydrogen bonded proton O….H-N[46] .

7
Figure 2.1H-NMR spectra of the complexes [I] and [II] in DMSO-d6.

3.4. X-ray structure of tris(hydroxymethyl)aminomethane)- (chloranilic acid)

complexes , I and II
The crystallographic studies on 1:1 and 1:2 complexes of chloranilic acid (CLA) with e-
donors such as amines, revealed various types of hydrogen bonding patterns formed
between CLA and amines, as well as between CLA`s [47, 48]. In this study, two
compounds of CLA with THAM, namely, [CLA(THAM)2] (I) and [CLA(THAM)]2 (II),
are isolated. Their crystal structures have been determined in order to study the hydrogen
bond formation. The crystal data and structure refinement parameters for (I) and (II) are
listed in Table 1 and their molecular structures are shown in Figs. 3 and 4, respectively. The
CLA molecules in the two compounds show a characteristic behavior. In structure (I), the
isolated CT complex of the composition [(CLA)(THAM)2] is crystallized in monoclinic
P21/c space group. The X-ray structure of CT complex together with the atomic numbering
scheme, Fig. 3, consists as a result of discrete molecular ionic unit in which the hydrogen
atoms of the hydroxyl groups of CLA were transferred to two N atoms of the two THAM

8
 molecules[(CLA)2-((THAM)2)2+] beside the formation of intermolecular hydrogen bond
between the hydrogen of one hydroxyl group of THAM with the oxygen of hydroxyl group
of CLA [O(9)-H(9)...O(2)]. On the other hand, the two THAM molecules in the crystal
lattice are linked together by three intermolecular hydrogen bonds between [N(1)-
H(11)...O(8)], [N(1)-H(11)...O(9)] and [O(9)-H(9)...O(2)]. The X-ray single crystal study
showed that the hydrogen bonds, of both O-H...O and N-H...O types, create very stable
networks which stabilize the crystal. Some selected bond distances and angles are listed in
Table 2 while both inter- and intra-molecular hydrogen bond distances and angles are given
in Table 3. A view of the molecular packing showing these types of hydrogen bonding is
shown in Fig.5. The protonated THAM molecules are hydrogen bonded to each other,
playing a double role, Fig. 5, as a proton donor involving the amino protons (H12 and
H22), and as a proton acceptor through the oxygen atom of the alcohol functional group;
O(2) and O(4). In such a way, the chains are joined together resulting in the formation of
three- dimensional network. It worth to mention that the proton transfer led to remarkable
change in both bond distance and angels especially for those that are close to the sites
involved in the hydrogen bonding interaction. As a result of these interactions the C2-O2 (
1.258 Å) and C1-C2-C3 bond angle (118.8o) became significantly shorter than their
corresponding in the free CLA (1.355 Å, 123.42 o)[16]. From the X-ray data of compound
(I), the acid–base interaction mechanism occurs through proton- transfer, in which the
hydrogen of CLA transferred to the NH2 of THAM forming NH3+ ion, forming a charge
transfer complex of the formula [(CLA)2-((THAM)2)2+].

Table 1. Crystal data and structure refinement for structures (I) and (II).
(I) (II)
Empirical formula C14 H24 Cl2 N2 O10 C20 H28Cl4 N2 O15
Formula weight 451.25 678.24
Temperature 293(2) K 293(2) K
Wavelength 0.71073 Å 0.71073 Å
Crystal system Monoclinic Orthorhombic
Space group P21/c P21212
Unit cell dimensions a = 9.5844(7) Å, α = 90°. a = 6.8791(8) Å, α = 90°.
b = 17.859(1) Å, β= 107.560(9)°. b = 18.389(2) Å, β= 90°
c = 11.4151(9) Å γ= 90°. c = 21.213(2) Åγ= 90°.
Volume 1862.8(2) Å3 2683.4(5Å3
Z 4 4

9
Density (calculated) 1.609 Mg/m3 1.679Mg/m3
Absorption coefficient 0.407 mm-1 0.520 mm-1
F(000) 944 1400
Crystal size 0.280 x 0.200 x 0.060 mm3 0.480 x 0.120 x 0.020 mm3
θ range for data collection 2.951 to 25.350°. 2.881 to 25.347°.
Index ranges -8<=h<=11, -16<=k<=21, - -3<=h<=8, -22<=k<=15, -
13<=l<=13 25<=l<=25
Reflections collected 6711 9833
Independent reflections 3407 [R(int) = 0.0222] 4898 [R(int) = 0.0448]
Completeness to theta = 25.242° 99.8 % 99.6 %
Absorption correction Semi-empirical from equivalents Semi-empirical from
equivalents
Max. and min. transmission 0.976 and 0.895 0.990 and 0.789
Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints / parameters 3407 / 26 / 72 4898 / 73 / 416
Goodness-of-fit on F2 1.025 1.037
Final R indices [I>2σ(I)] R1 = 0.0333, wR2 = 0.0714 R1 = 0.0848, wR2 = 0.1995
R indices (all data) R1 = 0.0511, wR2 = 0.0789 R1 = 0.1295, wR2 = 0.2177
Largest diff. peak and hole 0.211 and -0.221 e.Å-3 0.518 and -0.544 e.Å-3

10
Figure 3. X-ray molecular structure of [(CLA)(THAM)2] CT complex] (50%
probability ellipsoids).

Figure 4. X-ray molecular structure of [(CLA)(THAM)] CT complex] (50%

probability ellipsoids).

11
Figure 5. Packing diagram for (I),[(CLA)(THAM)2] CT complex viewed along the b axis,
showing the hydrogen-bonded layer structure

Figure 6. Hydrogen bonds in [(CLA)(THAM)]2.H2O, CT complex, II, and its crystal packing
diagram viewed along the b axis, showing the hydrogen-bonded layer structure

12
Table 2Bond lengths [Å] and angles [°] for [1(CLA):2(THAM)] CT complex.

Cl(1)-C(3) 1.7430(18) N(1)-H(13) 0.8497

Cl(2)-C(6) 1.7393(19) C(7)-C(10) 1.523(3)
O(1)-C(1) 1.242(2) C(7)-C(8) 1.523(3)
O(2)-C(2) 1.258(2) C(7)-C(9) 1.525(3)
O(3)-C(4) 1.243(2) O(8)-C(12) 1.406(2)
O(4)-C(5) 1.259(2) O(9)-C(13) 1.424(3)
O(5)-C(8) 1.419(2) O(10)-C(14) 1.401(4)
O(6)-C(9) 1.420(2) O(10')-C(14') 1.396(15)
O(7)-C(10) 1.420(2) N(2)-C(11) 1.497(2)
N(1)-C(7) 1.502(2) N(2)-H(21) 0.9112
N(1)-H(11) 0.9278 N(2)-H(22) 0.9314
N(1)-H(12) 0.9124 N(2)-H(23) 0.9406

O(1)-C(1)-C(6) 125.26(17) O(2)-C(2)-C(1) 117.17(16)

O(1)-C(1)-C(2) 116.86(16) C(2)-C(3)-Cl(1) 118.81(14)
O(2)-C(2)-C(3) 124.89(17) C(4)-C(3)-Cl(1) 117.77(14)
O(3)-C(4)-C(3) 125.51(18) O(4)-C(5)-C(4) 116.11(17)
O(3)-C(4)-C(5) 116.30(17) C(5)-C(6)-Cl(2) 117.42(14)
C(3)-C(4)-C(5) 118.17(17) C(1)-C(6)-Cl(2) 118.87(14)
O(4)-C(5)-C(6) 125.07(17)
N(1)-C(7)-C(10) 106.16(15) C(8)-C(7)-C(9) 111.78(16)
N(1)-C(7)-C(8) 106.26(15) O(5)-C(8)-C(7) 107.59(15)
C(10)-C(7)-C(8) 112.55(15) O(6)-C(9)-C(7) 112.59(16)
N(1)-C(7)-C(9) 109.12(15) O(7)-C(10)-C(7) 111.10(16)
C(10)-C(7)-C(9) 110.66(16)
N(2)-C(11)-C(12) 109.61(16) C(12)-C(11)-C(14) 104.19(19)
N(2)-C(11)-C(13) 107.48(17) C(13)-C(11)-C(14) 112.6(2)
C(12)-C(11)-C(13) 114.18(17) O(8)-C(12)-C(11) 113.34(17)
N(2)-C(11)-C(14) 108.69(17) O(9)-C(13)-C(11) 111.51(16)
O(10)-C(14)-C(11) 107.8(2)

13
Table 3 Intra- and intermolecular hydrogen bond distances and angles [Å and °]
for1(CLA):2(THAM)- CT complex.

D-H...A d(D-H) d(H...A) d(D...A) <(DHA)

O(6)-H(6O)...O(8) 0.81 2.11 2.872(2) 157.1
O(7)-H(7O)...O(1)#1 0.80 1.99 2.7891(18) 172.0
N(1)-H(11)...O(8) 0.93 2.40 2.889(2) 112.5
N(1)-H(11)...O(9) 0.93 2.07 2.969(2) 162.1
N(1)-H(12)...O(4)#2 0.91 1.85 2.751(2) 168.6
N(1)-H(13)...Cl(1)#3 0.85 2.77 3.4388(17) 136.7
C(8)-H(82)...Cl(2)#1 0.97 2.82 3.792(2) 176.1
C(9)-H(91)...O(10')#4 0.97 2.47 3.348(11) 150.6
O(8)-H(8O)...O(3)#2 0.80 2.36 3.086(2) 151.9
O(8)-H(8O)...O(4)#2 0.80 2.00 2.616(2) 133.6
O(9)-H(9O)...O(2) 0.80 2.04 2.837(2) 171.3
O(10)-H(10)...O(6)#5 0.82 2.05 2.866(2) 175.5
O(10')-H(10')...O(6)#5 0.82 2.54 2.996(12) 115.9
N(2)-H(21)...O(5)#6 0.91 2.02 2.924(2) 171.4
N(2)-H(22)...O(2)#3 0.93 2.07 2.964(2) 160.2
N(2)-H(23)...O(7)#3 0.94 1.87 2.801(2) 169.5
C(14)-H(142)...O(5)#5 0.97 2.51 3.429(3) 158.5
Symmetry transformations used to generate equivalent atoms:
#1 -x+2,-y,-z+1 #2 x,y,z+1 #3 -x+1,-y,-z+1 #4 x+1,y,z #5 x-1,-y+1/2,z-1/2 #6
x-1,y,z
On the other hand, in compound II, the isolated complex crystallizes in orthorhombic
P21212 space group. The X-ray crystal structure consists of asymmetric molecular unit
containing two crystallographically independent THAM molecules and two chloranilic
acid molecules ,Fig. 4. It is noticed that compound II is not involving a proton transfer
from CLA to THAM as observed in compound (I), instead, both the acid and base are
held together by mainly short O—H----O, N—H----O, as well as few C—H----O and one
C—H----Cl hydrogen bonds. The X-ray single crystal study shows that the hydrogen
bonds, of both O—H...O and N—H...O types, create very stable networks which stabilize
the crystal. Some selected bond distances and angles are listed in Table 4 while the inter-
and intra-molecular hydrogen bond distances and angles are given in Table 5. A view of
the molecular packing showing these types of hydrogen bonding is shown in Fig. 6.

14
Table 4 Bond lengths [Å] and angles [°] for 1(CLA):1(THAM) CT complex, II.
C(1)-O(1) 1.237(12) C(3)-Cl(2) 1.715(11)
C(1)-C(6) 1.370(14) C(4)-O(3) 1.314(13)
C(1)-C(2) 1.520(15) C(5)-O(4) 1.237(14)
C(2)-O(2) 1.200(13) C(6)-Cl(1) 1.716(11)
C(7)-O(5) 1.243(13) C(10)-O(7) 1.238(12)
C(7)-C(12) 1.437(14) C(10)-C(11) 1.490(15)
C(7)-C(8) 1.534(16) C(11)-O(8) 1.317(12)
C(8)-O(6) 1.221(13) C(11)-C(12) 1.339(15)
C(8)-C(9) 1.389(16) C(12)-Cl(3) 1.721(11)
C(9)-C(10) 1.379(15) C(13)-N(1) 1.493(13)
C(9)-Cl(4) 1.747(10) C(13)-C(15) 1.522(15)
C(13)-C(14) 1.531(17) C(17)-C(20) 1.51(2)
C(13)-C(16) 1.545(16) C(17)-C(18) 1.54(2)
C(14)-O(9) 1.420(14) C(17)-C(18') 1.56(2)
C(15)-O(10) 1.428(15) C(17)-C(19) 1.57(2)
C(16)-O(11) 1.431(14) C(17)-C(19') 1.58(2)
C(17)-N(2') 1.484(18) C(18)-O(12) 1.408(17)
C(17)-N(2) 1.490(19) C(18)-C(20) 2.00(4)
C(17)-C(20') 1.51(2) C(18')-O(12') 1.40(2)
C(19)-O(13) 1.320(19)
C(19')-O(13) 1.33(2)
C(20)-O(14) 1.24(3)
C(20')-O(14) 1.34(2)
N(1)-H(11N) 0.8595
N(1)-H(12N) 0.8595
N(2)-H(21N) 0.8632
N(2)-H(22N) 0.8615

O(1)-C(1)-C(6) 125.0(10) O(7)-C(10)-C(11) 115.6(10)

O(1)-C(1)-C(2) 115.2(9) C(9)-C(10)-C(11) 116.5(10)
C(6)-C(1)-C(2) 119.8(9) O(8)-C(11)-C(12) 121.3(10)
O(2)-C(2)-C(3) 121.9(11) O(8)-C(11)-C(10) 114.8(9)
O(2)-C(2)-C(1) 120.6(10) C(12)-C(11)-C(10) 123.0(10)
C(4)-C(3)-Cl(2) 121.5(9) C(11)-C(12)-C(7) 120.1(10)
C(2)-C(3)-Cl(2) 118.0(8) C(11)-C(12)-Cl(3) 121.0(8)
O(3)-C(4)-C(3) 123.5(10) C(7)-C(12)-Cl(3) 118.7(8)
O(3)-C(4)-C(5) 115.4(9) N(1)-C(13)-C(15) 107.5(9)
O(4)-C(5)-C(6) 126.1(10) N(1)-C(13)-C(14) 108.7(9)
O(4)-C(5)-C(4) 114.6(10) C(15)-C(13)-C(14) 112.0(9)
C(1)-C(6)-Cl(1) 120.8(8) N(1)-C(13)-C(16) 106.8(8)
C(5)-C(6)-Cl(1) 117.0(8) C(15)-C(13)-C(16) 111.9(9)
O(5)-C(7)-C(12) 122.7(11) C(14)-C(13)-C(16) 109.8(10)
O(5)-C(7)-C(8) 118.5(10) O(9)-C(14)-C(13) 113.3(10)
C(12)-C(7)-C(8) 118.5(9) O(10)-C(15)-C(13) 108.1(10)
O(6)-C(8)-C(9) 125.3(11) O(11)-C(16)-C(13) 112.6(9)
O(6)-C(8)-C(7) 118.1(10) N(2')-C(17)-C(20') 104.7(15)
C(9)-C(8)-C(7) 116.6(10) C(20)-C(17)-C(18) 81.9(17)
C(10)-C(9)-C(8) 124.9(10) N(2)-C(17)-C(18') 107.2(16)
C(10)-C(9)-Cl(4) 117.2(9) C(20)-C(17)-C(19) 113.6(17)
C(8)-C(9)-Cl(4) 117.9(8) C(18)-C(17)-C(19) 155.0(17)
O(7)-C(10)-C(9) 127.8(10) N(2')-C(17)-C(19') 108.5(16)

15
C(20')-C(17)-C(19') 111.0(18) C(17)-C(20)-C(18) 49.7(11)
O(12)-C(18)-C(17) 109.1(16) O(14)-C(20')-C(17) 118.4(17)
O(12)-C(18)-C(20) 114(2) C(13)-N(1)-H(11N) 120.3
C(17)-C(18)-C(20) 48.4(11) C(13)-N(1)-H(12N) 119.7
O(12')-C(18')-C(17) 114.3(17) H(11N)-N(1)-H(12N) 120.0
O(13)-C(19)-C(17) 114.9(15) C(17)-N(2)-H(21N) 101.2
O(13)-C(19')-C(17) 114.0(16) C(17)-N(2)-H(22N) 96.2
O(14)-C(20)-C(17) 125(2) H(21N)-N(2)-H(22N) 78.5
O(14)-C(20)-C(18) 150(2)

Table 5 Intra- and intermolecular hydrogen bond distances and angles [Å and °] for
1(CLA):1(THAM)- CT complex, II.
D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
C(14)-H(14A)...Cl(1)#1 0.97 2.82 3.744(14) 160.6
C(19')-H(19D)...O(4)#1 0.97 2.60 2.99(3) 104.4
C(20)-H(20B)...O(6)#2 0.97 2.38 2.96(3) 117.5
C(20)-H(20B)...O(12) 0.97 2.40 2.88(3) 110.0
C(20')-H(20C)...O(6)#2 0.97 2.44 3.02(3) 117.4
C(20')-H(20D)...O(3)#3 0.97 2.50 3.42(3) 158.5
N(1)-H(11N)...O(15) 0.86 2.38 2.833(13) 113.6
N(1)-H(12N)...O(1)#4 0.86 2.37 2.999(11) 130.7
N(1)-H(12N)...O(2)#4 0.86 2.08 2.861(12) 151.5
N(2)-H(21N)...O(7) 0.86 1.91 2.73(3) 158.7
N(2)-H(22N)...Cl(4) 0.86 2.72 3.52(2) 156.4
N(2')-H(22')...O(7) 0.86 1.98 2.74(2) 146.7
O(1)-H(1O)...N(1)#5 0.82 2.28 2.999(11) 146.7
O(1)-H(1O)...O(2) 0.82 2.18 2.660(11) 117.8
O(3)-H(3O)...O(4) 0.82 2.09 2.565(11) 117.1
O(3)-H(3O)...O(14)#1 0.82 2.22 2.989(11) 156.2
O(6)-H(6O)...O(5) 0.82 2.23 2.703(13) 117.1
O(6)-H(6O)...O(12)#6 0.82 2.13 2.88(2) 152.4
O(6)-H(6O)...O(12')#6 0.82 2.08 2.84(2) 154.7
O(8)-H(8O)...O(7) 0.82 2.11 2.581(10) 116.2
O(8)-H(8O)...O(10) 0.82 1.96 2.663(11) 143.9
O(9)-H(9O)...O(15)#3 0.82 2.04 2.768(13) 148.7
O(10)-H(10O)...O(8) 0.82 1.92 2.663(11) 151.0
O(11)-H(11O)...O(15) 0.82 2.50 3.238(13) 150.5
O(11)-H(11O)...O(15)#7 0.82 2.45 2.766(11) 104.4
O(11)-H(11O)...N(1) 0.82 2.62 2.938(12) 105.0
O(12)-H(12O)...O(5)#2 0.82 2.44 2.999(18) 126.1
O(12)-H(12O)...O(6)#2 0.82 2.10 2.88(2) 160.3
O(13)-H(13O)...O(4)#1 0.82 2.12 2.635(11) 120.6
O(14)-H(14O)...O(6)#2 0.82 2.08 2.798(11) 146.4
O(15)-H(151)...O(1)#8 0.83 2.20 2.787(11) 127.4
O(15)-H(152)...O(9)#9 0.83 2.31 2.768(13) 115.3
Symmetry transformations used to generate equivalent atoms:
#1 -x+1,-y,z #2 -x+1/2,y-1/2,-z+1 #3 x-1,y,z
#4 x-1/2,-y+1/2,-z #5 x+1/2,-y+1/2,-z #6 -x+1/2,y+1/2,-z+1
#7 -x+1,-y+1,z #8 -x+3/2,y+1/2,-z #9 x+1,y,z

16
 3.5. UV–vis absorption spectra

3.5.1. UV–vis absorption spectral characterization of the CT complexes

The UV–vis absorption spectra of the free acceptor (CLA) and free donor (THAM) in
methanol, as well as charge transfer complexes in 1:1 and 1:2 molar ratios are recorded as
methanol, ethanol or acetonitrile solutions, at room temperature, Fig. 7. The spectra of
CT-complexes show strong absorption band centered at ca.523, 527 and 516 nm in
methanol, ethanol and acetonitrile, respectively. These absorption bands are associated
with the strong change in color observed upon mixing of the reactants which reflect the
electronic transitions in the formed CT-complexes. A red shift of the position of the
charge transfer band from 523 nm and 527 nm in protic solvents (MeOH or EtOH,
respectively) to 516 nm in the aprotic solvent (acetonitrile) is observed reflecting the
sensitivity of the CT-complex formation to the solvent polarity. Furthermore, the
absorptions characteristic of the free CLA at 301, 304 and 296 nm are red shifted to 319,
321 and 302 nm in methanol, ethanol and acetonitrile, respectively upon complex
formation. Fig. 7 b and c shows that using either 1:1 or 1:2 (CLA: THAM) mole ratio in
methanol, ethanol or acetonitrile, the absorbance of the formed CT complex increases at
same λmax with a similar behavior, suggesting the formation of only one CT complex in
solution.

0 2 4 6 8 10
0.20 0.30
methanol CT complex
(b) (c)
2.5 (a) Ethanol
Methanol
-4 Ethanol
2x10 CLA Acetonitril 0.25
Acetonitrile
-4
2.0 2x10 THAM 0.15

0.20

1.5
Abs.
Abs.

Abs.

0.10 0.15

1.0
0.10

0.05
0.5 0.05

0.0 0.00 0.00

200 300 400 500 600 400 450 500 550 600 650 700 350 400 450 500 550 600 650

λ(nm) λ(nm) Wavelengh nm

17
3.5.2. Molecular composition (Stoichiometric ratios) of the formed CT complexes

The molecular composition of the formed complex in different solvents was estimated
using the continuous variations Job`s method [49], at room temperature. Fig. 8, represents
the continuous variation plots of different mole ratios acceptor/donor , as methanol,
ethanol or acetonitrile solutions. The spectral features indicates the formation of only 1:1
CT complex , whatever the mole ratio. Consequently, it is concluded that the solvent
polarity as well as the reactants mole ratio do not affect the complex molecular
composition in solutions, which is not the behavior in the solid state CT complex,
Scheme 1.

1.4 EtO H
M eO H
1.2 AN

1.0
Abs

0.8

0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
n THAM /(n THAM +n CLA )

Figure 8. Job's method of continues variations of the formed CT complex THAM-

CLA in methanol, ethanol and acetonitrile, at room temperature.
3.5.3. Effect of reactant concentration on CT complex formation

The effect of increasing the concentration of electron donor (THAM) in presence of

constant concentration of electron acceptor(CLA) was investigated by measuring the
absorbance of the CT complex in methanol, ethanol or acetonitrile, Fig. 9. It is observed
that the absorbance of the CT complex in all solvents increases with increasing donor
concentration at same λmax of the complex, indicating the formation of stable CT complex
18
 in the different solvent. The spectra in all solvents show an isosbestic point characteristic
of the formation of 1:1 proton transfer equilibrium between CLA and THAM in
equation(2).

1.4
-5 -4
5.0x10 5.0x10
-5 1x10
0.5 -4 Methanol 0.6 1.3
2x10
-4
1x10 1x10
-4
Ethanol Acetonitrile -4
-4 1.2 3x10
1.5x10 1.5x10
-4
-4
-4 1.1 4x10
2x10 0.5 2x10
-4
5x10
-4

0.4 2.5x10
-4
-4 1.0 -4
2.5x10 6x10
-4 -4
3x10 3x10
-4
0.9 7x10
-4 0.4 8x10
-4
3.5x10 3.5x10
-4
-4
0.8 -4
0.3 4x10 -4 9x10
Abs.

Abs.

Abs.
4x10 0.7 -3
-4 1x10
4.5x10 0.3 4.5x10
-4

5x10
-4
-4 0.6
5x10
0.2 -4
5.5x10 -4 0.5
5.5x10
0.2
0.4
0.3
0.1
0.1 0.2
0.1
0.0 0.0 0.0
350 400 450 500 550 600 650 350 400 450 500 550 600 650 350 400 450 500 550 600 650
Wave number nm Wave number nm Wavenumber nm

HCLA + H2N-R ↔ HCLA ---- H2N-R ↔ CLA- ----H+NH2R (2)

Figure 9. Effect concentration of the formed CT complex of 5.00x10-4mol/dm3 CLA
with various concentrations of THAM from 1.00 x10-4 to 1.00x10-3 mol/dm3
in methanol, ethanol and acetonitrile, at room temperature.

3.5.4. Effect of reaction time on CT complex formation

The effect of time on the CT-complex formation was studied by mixing 1.0×10−3 M from
each of THAM and CLA (1:1 molar ratio) in the methanol, ethanol and acetonitrile
solvents. It has been found that the absorbance of the CT-complex reached maximum and
constant value instantly in all solvents confirming that the complex absorbance is time
independent, Fig. 10. The absorption value of the CT-complex didn`t change within two
hours confirming its stability attributable to the strong bonding between CLA and THAM
moieties.

19
 1 .0
M e th a n o l
0 .9 E th a n o l
A c e to n itrile
0 .8

0 .7

0 .6
Abs.

0 .5

0 .4

0 .3

0 .2

0 .1

0 .0
0 10 20 30 40 50 60 70 80 90 100 110 120
T im e ( m i n . )

Figure 10. Effect of time on 1(CLA):1(THAM)- CT complex in methanol, ethanol

and acetonitrile, at room temperature.
3.5.5. Formation constant of the CT complex (KCT)

Based on the electronic spectra of the formed complexes at various concentrations of the
donors in different solvents, KCT, are determined by using the minimum–maximum
absorbance method[45] and the results are collected in Table 6. Generally, The high KCT
values indicate the stability of CT-complex formed. The data in Table 6, show that the
KCT is strongly dependent on the solvent used with the order: ethanol > methanol >
acetonitrile. The least polar aprotic solvent, acetonitrile, exhibits the smallest value of the
formation constant relative to both polar protic solvents, methanol and ethanol, due to
electric permittivity of the investigated solvents.

Table 6. Room temperature- minimum–maximum absorbance data for CLA-THAM CT-

complex formation in; methanol, ethanol and acetonitrile solvents

λmax C-THAM KCT Average

Solvent Amin Amax
(nm) (mol/dm3) Acomplex KCT
0.00015 0.19665 649.5264
0.0002 0.23487 1154.321
0.00025 0.2901 2055.502
Methanol 523 0.15633 0.50703 5693.698
0.00035 0.33049 2818.625
0.0004 0.43172 8126.116
0.00045 0.47419 19358.1
0.00015 0.2704 787.272
Ethanol 527 0.21827 0.60148 6825.297
0.0002 0.31527 1355.648

20
 0.00025 0.36256 2013.087
0.0003 0.41853 3127.474
0.00035 0.46194 4365.594
0.0004 0.4986 6055.167
0.00045 0.53262 9130.119
0.0005 0.55933 14711.96
0.00055 0.57184 19881.35
0.00025 0.35682 432.9917
0.00035 0.49857 881.6489
0.00045 0.61644 1200.142
0.0005 0.7414 1791.115
Acetonitrile 516 0.25659 1.28275 3371.368
0.0006 0.9124 2951.307
0.0007 1.01877 4124.663
0.0008 1.1281 7044.213
0.0009 1.16467 8544.866

The formation of intermolecular hydrogen bonding between the hydroxylic solvents,

methanol and ethanol with THAM gives extra stability of the formed complex which
cause high formation constants relative to acetonitrile. Moreover, the high electric
permittivity of acetonitrile hinders the hydrogen bonded charge transfer reaction between
THAM and CLA due to the formation of dimeric acetonitrile molecules leading to
decrease of KCT [11]. On the other hand, the pKa of THAM (8.08) and the high acidity
of CLA (pK1 = 1.07, pK2 = 2.24) permit the formation of proton transfer hydrogen
bonding beside the CT.

3.6. Computational methods

One of the most important theoretical approaches is the density functional theory (DFT),
which has a major role in investigation of the electronic properties and geometric
structure of the molecules [50-53]. All theoretical calculations were performed using the
Gaussian 03 program [54] applying the density functional theory with Becke’s three
parameter exchange function[41],[40], the Lee-Yang-Parr correlation functional
(B3LYP) with basis set 6-31G (d,p). Such combination gives a good result for systems
containing hydrogen bonds [55]. Some important parameters are calculated from the

21
optimized structure such as optimization energy, bond lengths, bond angles, reactivity
parameters and HOMO, LUMO energies. Chem 3D and Chemcraft programs [56]help in
extraction of some calculation results and visualize the optimized structures and the
frontier molecular orbitals (FMOs). Density of state (DOS)[57]is applied using Gauss-
Sum 3.0 python program [58] to illustrate the molecular orbital contribution and give
information about the stability of molecules in gas and liquid states.

3.6.1. Geometry Optimization

The optimized structure of CT complexes, I and II are shown in Figs. 11 and 12. The
calculated geometric parameters at B3LYP/6-31G (d,p) are given in Table 7. The B3LYP
calculated values are in agreement with the experimental data with slight differences in
the bond lengths and angles. This is attributed to run optimization in isolated gaseous
phase while the experimental X-ray results are given for the solid phase. The calculated
data and Fig. 11 indicate that the proton transfer from OH`s (O2 and O4) in CLA to the
amino nitrogen atoms (N2 and N1) of two THAM molecules, leaving a protonated amino
groups in CT complex, I. The studied structure also shows formation of intermolecular
hydrogen bonds between the proton leaved oxygen (negatively charged) in the acid and
the hydrogen of hydroxyl group in THAM. On the other hand, the calculated data for
complex II, Fig. 12, show a number of intermolecular hydrogen bonds, without proton
transfer.

22
 Figure11. The optimized structure of [(CLA)(THAM)2] complex, I.

Figure12. The optimized structure of 1(CLA):1(THAM) complex, II.

Table 7. Theoretical geometrical parameters for 1(CLA):2(THAM) and 1(CLA):1(THAM)

complexes with B3LYP/6-31G(d,p)
Structural 1(CLA):1(THAM) 1(CLA):2(THAM)
parameters
Bond length (Ao)
C1 – O1 1.224 1.229
C2 – O2 1.311 1.331
C4– O3 1.218 1.223
C5 – O4 1.329 1.434
C3 – Cl1 1.737 1.738
C6 – Cl2 1.750 1.726
C1 – C2 1.518 1.522
C2 – C3 1.365 1.356

23
 C3 – C4 1.463 1.459
C4 – C5 1.521 1.510
C5 – C6 1.356 1.359
C7 – N1 ---- 1.515
C11 – N2 1.491 1.473
O2 --- H1 (H-bond) 1.976 1.679
O2-H2 1.089 ------
N1 – H5 ------ 1.021
N1 – H6 ------ 1.044
N1 – H7 ------- 1.037
N2 --- H2 (H-bond) 1.466 1.018
N2 – H3 1.019 1.019
N2 – H4 1.020 0.999
Bond angle (o)
O1 – C1 – C2 119.39 118.93
O2 – C2 -C3 122.85 125.93
O3 – C4 – C5 118.79 117.07
O4 – C5 – C4 113.43 114.24
Cl1 – C3 – C2 120.50 121.58
Cl2 – C6 – C1 117.86 118.06
C2 – O2 ---H1 144.18 133.79
H2 – N2 – H4 110.83 110.80
H2 – N2 – H3 105.48 110.01
H3 – N2 – H4 106.47 108.23
H5 – N1 – H6 ------ 148.83
H5 – N1 – H7 ------- 106.76
H6 – N1 – H7 ------- 112.16
C13 – O9 – H1 108.92 103.12

TD-DFT at 6-31G(d,p) method was applied on the optimized ground state structures of
complexes, I and II, considering PCM model, in methanol, to predict the electronic
absorptions, Fig.13. [(CLA)(THAM)2], I, shows two electronic absorption maxima; at
328 (f = 0.085 , E= 3.74 eV) corresponding to π- π* transition for 68.8% contribution of
HOMO-1→LUMO+2 and 7.8% contribution of HOMO →LUMO+3 transitions and 525
nm (f = 0.025, E= 2.35 eV) corresponding to n-π* transition for 97% contribution of
HOMO→LUMO. [(CLA)(THAM)], II, shows two electronic absorption spectra at 345
nm (f = 0.086, E= 3.58 eV) corresponding to π- π* transition for 51.8% contribution of
HOMO-1→LUMO and 1.9% contribution of HOMO→LUMO+2 transitions and 535 nm
(f = 0.011, E= 2.33 eV) corresponding to two contributions for 70.56% contribution of
HOMO-1→LUMO and 12.5% HOMO→LUMO+3. The results show a good approach to
the experimental data. Figs. 14 a and 14b show singlet transitions of molecular orbitals
for [(CLA)(THAM)2], I and [(CLA)(THAM)], II respectively, using TD-DFT(B3LYP).
For both complexes, the orbital contribution on the interacting centers began to appear in
HOMO, HOMO-1 and HOMO-2 and in LUMO , LUMO+1 and LUMO+2 , in confirm
with the higher activity of CLA moiety [10].

24
Figure13. Calculated electronic absorption spectra with oscillator strength using
TD-DFT (B3LYP) in methanol for (a) complex I and (b) complex II

HOMO HOMO -1 HOMO -2

LUMO LUMO+1 LUMO+2

LUMO+3 LUMO +4

Figure 14a . Singlet transitions of molecular orbitals for [(CLA)(THAM)2], I using

TD-DFT(B3LYP)

25
 HOMO HOMO -2
HOMO -1

LU
MO

LUMO+3
LUMO +2

Figure 14 b. Singlet transitions of molecular orbitals for [(CLA)(THAM)], II using

TD-DFT(B3LYP)

3.6.2. Quantum and reactivity studies

The energies of the HOMO and LUMO-orbitals are evaluated for complex I and II
optimized structures in gas phase and in methanol. The reactivity parameters values such
as ionization potential (IP), chemical hardness (η), chemical potential (µ), electron
affinity (A), global chemical softness (σ) and energy fraction (X) are obtained and
tabulated in Table 8. Most of parameters values predict the higher stability of complex I
over complex II, in gas phase. These calculated parameters give various aspects of
reactivity associated with chemical reactions [59, 60]. Also total energy (E a.u.), nuclear
repulsion energy NRE (Hartees) and dipole moment (D) tabulated in Table 8, give
information about the charge separation between atoms in gas phase and solution.

Definitions for some parameters are provided by the following equations:

IP = - EHOMO (3)

A = - ELUMO (4)

η = (IP-A)/2 (5)

µ = - (IP+A)/2 (6)

26
 σ = 1/ η (7)

EGAP = ELUMO- EHOMO (8)

X = EHOMO / ELUMO (9)

The difference in values of EHOMO and ELUMO (i.e. EGAP) for the structures in gas and
methanolic solutions state indicate that the structures of complexes; I and II in gas phase
are more stable than in solution. The chemical potential represents the electronegativity
of the compound which is a parameter that may indicate the direction of electron flow.
Complex I in gas phase displays more negative chemical potential value that is referred to
transfer of 2 protons from CLA to nitrogen atoms of 2 THAM molecules which is not the
case in complex II .
Table 8. Quantum and reactivity parameters of ; 1(CLA):2(THAM), complex I and
1(CLA):1(THAM), complex II, in gas phase and in methanol

1(CLA):1(THAM) 1(CLA):2(THAM)
Parameter
Gas Methanol Gas Methanol

E -1890.57 -1888.38 -2444.99 -2441.78

NREa 1916.67 1924.89 3675.22 3735.97

D 6.78 25.69 9.72 13.73

EHOMO -7.83 -5.53 -9.69 -8.52

ELUMO -4.38 -2.07 -7.39 -4.55

EGAPb 3.45 3.46 2.30 3.98

IP 7.83 5.53 9.69 8.52

A 4.38 2.07 7.39 4.55

µ -6.105 -3.80 -8.54 -6.53

η 1.73 1.73 1.15 1.99

σ 0.58 0.58 0.87 0.50

X 1.79 2.67 1.31 1.87

27
Notes: (a) 1 Hartree = 4.35974417 x10–18 J = 27.2113845 eV, (b) EGAP= ELUMO - EHOMO

3.6.3. Mulliken atomic charge distribution

The main Mulliken atomic charge densities of the titled complexes, I and II, in gas phase
are given in Table 9. The relatively large negative charge density value on oxygen atom
(O2) of CLA (-0.554 e) in complex I, indicates its hydrogen bonding with the H1 on O9
of THAM (-0.55 e), with proton transfer to nitrogen atom. The positive charges on
N1(0.386) and N2(0.411) agree with the experimental results of N-donation towards the
positive center of proton transfer H-bond. Furthermore, the higher positive charges on
H1, H2, H3 and H7 (0.361, 0.351, 0.340 and 0.365) confirm formation of hydrogen bond
with O2, O8, O8 and O9, respectively. While in case of complex II, the charge density on
O2, is found to be lower negative value (- 0.433 e) than in case of complex I, confirming
hydrogen bond with H1 on O9 (-0.55 e), without proton transfer. The N2 atom exhibits a
negative charge (-0.670 e) giving further evidence for the absence of proton transfer.
However, the negative charge density on O1 (-0.488 e) indicates its hydrogen bonding
with the H2 on O2 (-0.55 e). The charge on C3 and C6 (0.233e, 0.239e) confirm the
presence of electron delocalization around the ring (i.e. presence of resonance structure
between O1 and C3, O4 and C6).

Table 9. Mulliken atomic charge distribution of some centers in CLA-THAM

complexes; I and II, in gas phase
Atom [(CLA) (THAM)2], I [(CLA) (THAM)],II Atom [(CLA) (THAM)2], I [(CLA) (THAM)],II
Cl1 0.051 0.016 C7 0.041 -
Cl2 0.096 0.032 C8 0.069 -
O1 -0.488 -0.488 C9 0.054 -
O2 -0.554 -0.433 C10 0.094 -
O3 -0.460 -0.487 C11 0.035 0.077
O4 -0.484 -0.418 C12 0.055 0.059
O5 -0.534 - C13 0.165 0.073
O6 -0.595 - C14 0.036 0.056
O7 -0.586 - N1 0.386 -
O8 -0.609 -0.553 N2 0.411 -0.670

28
O9 -0.550 -0.550 H1 0.361 0.338
O10 -0.562 -0.574 H2 0.280 0.284
C1 0.465 0.382 H3 0.351 0.290
C2 0.340 0.448 H4 0.340 0.119
C3 -0.233 -0.255 H5 0.291 -
C4 0.449 0.336 H6 0.331 -
C5 0.362 0.430 H7 0.365 -
C6 -0.239 -0.247

3.6.6. Density of state (DOS) spectra

DOS of a system describes the number of states per an interval of energy at each energy
level available to be occupied [61]. The results were obtained with Gauss Sum 3.0
program[62]. DOS spectra of complexes ,I and II in gas phase are shown in Fig. 15. It is
found that the difference in energy between HOMO and LUMO of complex
II,[(CLA)(THAM)], 3.45 eV, is higher than complex I, [(CLA)(THAM)2], 2.30 eV. The
energy gap values of the two complexes indicates the higher stability of complex I
relative to complex II in the gaseous state. On the other hand, DOS spectra in methanol
gives an opposite results, Fig. 16, where the difference in HOMO and LUMO energies of
complex II, 3.46 eV, is lower than that of complex I, 3.98 eV. Therefore it can be
concluded that the higher probability of complex II formation in methanol is more than of
formation of complex I.

29
Figure 15. DOS spectra of (a) [(CLA)(THAM)],II with EGAP =3.45 eV and (b) [(CLA)(THAM)2,I
with EGAP =2.30 eV complexes in gas phase

a b

30
Figure 16. DOS spectra of (a) [(CLA)(THAM)], II, EGAP= 3.46 eV and (b) [(CLA)(THAM)2] ,I,
EGAP= 3.98 eV in methanol

Conclusion
Two new charge transfer complexes, [(CLA)(THAM)2], I and [(CLA)(THAM)]2.H2O, II
were synthesized and characterized using different physicochemical tools. Single-crystal
X-ray crystallography indicated the formation of both inter- and intra-molecular
hydrogen bonding. In addition, complex [II] exhibits only charge transfer while complex
[I] exhibits both charge and proton transfer. The UV-Vis electronic spectra confirmed the
stoichiometric ratio of the formed complexes to be 1:1 in the different solvents utilizing
Job's method. The formation constant KCT, was estimated giving high values in the order,
Ethanol > Methanol >> Acetonitrile, indicating the stability of CT-complexes. The TD-
DFT with PCM as solvation model was applied. Geometrical parameters, optimized bond
distances, Mulliken atomic charges, molecular potential energy surface, HOMO and
LUMO of the formed complexes showed strongly consistent with the experimental
results and appeared to indicate that the stabilities of the studied complexes are resultant
of proton and charge transfers.

Appendix A. Supplementary data

CCDC 1910603 and 1910599 contain the supplementary crystallographic data for the two
CT complexes [I] and [II] respectively. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html,or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-
mail: deposit@ccdc.cam.ac.uk.

31
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35
Highlights
• Crystal and molecular structure of two new synthesized charge transfer complexes.
• Spectral properties of the CLA-THAM complexes formed in mole ratios; 2:1 and 1:1.
• Spectroscopic analysis revealed the 1:1 mole ratio formation in different solvents.
• Computational study of synthesized CT complexes.