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Karbala International Journal of Modern Science 4 (2018) 258e273
http://www.journals.elsevier.com/karbala-international-journal-of-modern-science/

Aging effect on bonding properties of fluorescent neodymium

materials
Iffat Ameen, Abhishek Kumar Tripathi, Raj Laxmi Mishra, Afshan Siddiqui,
Umesh Nath Tripathi*
Department of Chemistry, D. D. U. Gorakhpur University, Gorakhpur, UP India
Received 8 February 2018; revised 9 April 2018; accepted 5 May 2018
Available online 26 May 2018

Abstract

The neodymium complexes with nitrogen and oxygen donor pyrazoline ligands were synthesized by the conventional method.
To observe the effect of the change in environment, the mixed ligand complexes along with pure neodymium-pyrazoline complexes
were synthesized. Shelf-life of these newly synthesized materials was studied by the absorbance spectral peaks, whereby the aging
effect was clearly seen in all these neodymium complexes. Considering the effect of time and shelf-life, the neodymium-pyrazoline
complexes show comparatively lower stability than the mixed ligand complexes of neodymium. The detailed characteristics of
these newly synthesized materials are presented in this manuscript.
© 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Keywords: Neodymium; Pyrazoline; Mixed ligand complexes; Aging

1. Introduction known to have the luminescence property with

The lanthanide complexes seem to seek the atten-
tion in its designing and synthesis due to its potential
properties in different fields. Lanthanides are well
known to have optical properties [1e6] used in the
field of optoelectronic technology [7], optical
communication system and amplifiers [8], backlights
[9], mechanoluminescence, bioscience and bio imag-
ing [2,10e21], solar energy conservation and tech-
nology [22e26] etc. The rare earth complexes are well
* Corresponding author.
E-mail address: un_tripathi@yahoo.com (U.N. Tripathi).
Peer review under responsibility of University of Kerbala.
different ligands [27,28] as well as in doped materials
[29]. The luminescence property is somehow related to
the less known redox behavior of the inner transition
elements [30]. After the synthesis and structural
determination, the stability of the rare earth complexes
is of considerable interest. The thermodynamic stabil-
ity [31], mechanical resistance, stability towards the
chemicals and the thermal resistance [32e37] are well
explained in the literature. Comparatively less attention
has been devoted to the stability of the complexes with
respect to time. Zheng et al. discussed the time
dependent dielectric properties of neodymium-
ceramics with the help of XRD pattern [38]. By
perceiving the importance of rare earth complexes in
diverse field, we have taken here an example of

https://doi.org/10.1016/j.kijoms.2018.05.001
2405-609X/© 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273
neodymium to study the most important fluorescence
behavior. The stability of the complexes, the bonding
and structural properties, were taken as an important
phenomenon to consider these fluorescent active neo-
dymium complexes at commercial level. Stability with
respect to time and high quantum yield, make these
materials of high commercial value.
2. Material and methods
All the solvents (benzene, methanol, ethanol etc.)
were rigorously dried and purified by standard methods
before use [39]. The chemicals used are of analytical
grade. Neodymium chloride hexahydrate (HPLC), so-
dium diethyldithiocarbamate (S.D. Fine), o-hydrox-
yacetophenone (CDH) and benzaldehydes (E. Merk)
were used as received. Pyrazolines and potassium ethyl
xanthate were prepared by the reported methods
[40,41].
2.1. Synthesis of metal-pyrazoline complexes by 1:1 M ratio
of metal chloride and pyrazoline ligand
Freshly cut pieces of sodium metal were taken with
excess of isopropanol and refluxed for about 30 min
until a clear solution of sodium isopropoxide was ob-
tained. The benzene solution of 3(2-hydroxyphenyl)-5-
(4-substituted phenyl) pyrazoline was added in the
above prepared sodium isopropoxide and the reaction
mixture was further refluxed for 2 h, whereby a yellow
colored solution was obtained. The content was cooled
to room temperature after that, methanolic solution of
metal chloride was added with constant stirring. The
stirring continued for about 2 h, till the color of the
reaction mixture underwent a change from greenish
yellow to greenish brown. The reaction mixture was
filtered to remove precipitated NaCl. The solvent was
removed under reduced pressure from the filtrate
whereby dirty greenish brown solid was obtained.
Complex 1e4 were prepared by this procedure
[Reaction Scheme 1].
NdCl3.6H2O + [C15H12N2OX]Na
Reaction Scheme 1. Synthesis of Neodymium-Pyrazoline complex.
[NdCl2(C15H12N2OX).nH2O] + Na[C5H10NS2].3H2O
[NdCl2(C15H12N2OX).nH2O] + K[C2H5OCS2]
Reaction Scheme 2. Synthesis of Neodymium-pyrazoline-diethyldithiocarbamate and Neodymium-pyrazoline-ethylxanthate complex.
259
2.2. Synthesis of mixed ligand complexes of metal chloride
with pyrazoline and diethyldithiocarbamate/ethylxanthate in
1:1:1 M ratio
The mixed ligand complexes of neodymium with
diethyldithiocarbamate and ethylxanthate were pre-
pared by two steps. In first step, a methanolic solution
of neodymium chloride was added in benzene solution
of pyrazoline and refluxed for about 6 h. The color of
solution underwent change, after that, the content was
cooled at room temperature. In second step, the
methanolic solution of sodium diethyldithiocarbamate/
potassium ethylxanthate was added in the above con-
tent and stirred for about 8e9 h at room temperature.
The reaction mixture was filtered to remove the
precipitated NaCl or KCl. The solvent was reduced
from the filtrate in vacuum, which yielded some
insoluble colored material, which was finally separated
by filtration. The solid thus obtained was washed with
water. The complex 5e12 were prepared by this
method [Reaction Scheme 2].
3. Characterization measurements
For the determination of molecular weights, the
molecular ion peak was detected by DART mass
spectra on a JMS-T100LC Accu TOF mass spec-
trometer. The accelerating voltage was 10 kV and
spectra were recorded at room temperature. Elemental
analysis (C, H, N and S) were carried out on an Ele-
mentar Vario EL III C, H, N, S analyzer. Chlorine was
estimated by Volhard's method [42]. Oxygen was
analyzed by EuroVector elemental analyzer. Neo-
dymium is estimated as Nd2O3 by reported analytical
method [43]. IR spectra were recorded on Thermo
Nicolet Fourier Transform Infrared Spectrometer
(Model: 6700) in the range 5000e50 cm
1. Electronic
spectra were recorded in dichloromethane on Varian,
Cary 5000 UVevisible spectrophotometer within the
range 1000e230 nm. Scanning electron microscopy
(SEM) studies have been carried out on JEOL
[Nd(C15H12N2OX)Cl2.nH2O] + NaCl
[Nd(C5H10NS2)(C15H12N2OX)Cl.nH2O] + NaCl
[Nd(C2H5OCS2)(C15H12N2OX)Cl.nH2O] + KCl
260 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273
scanning electron microscope (Model JSM-6390LV)
at magnification 5 to 300,000 (Both High and
Low Vacuum Models). X-ray diffraction studies were
carried out on model Bruker AXS D8 Advance
diffractometer at temperature range
170  C to
þ450  C. Thermogravimetric analysis for the com-
plexes has been carried out using Perkin Elmer TGA
instrument. Luminescence studies have been done by
Jobin Yvon spectrofluorimeter in the range
200e800 nm. Life time system was carried out on
JOBIN-VYON fluorocube.
4. Results and discussion
The complexes of type [Nd(C15H12N2OX)(2H2O)
Cl2]$H2O are brownish-green colored solid while
mixed ligand complexes having type [Nd(C5H10
NS2)(C15H12N2OX)(2H2O)Cl] and [Nd(C2H5OCS2)
(C15H12N2OX)(4H2O)Cl]$H2O are greenish-brown
and soil colored solids respectively. All these com-
plexes are non-hygroscopic, stable at room temperature
and soluble in solvents like, dimethylformamide,
dichloromethane etc. Molecular weight measurements
show that these complexes are monomeric in nature
(see Fig. 1). The elemental analysis (C, H, N, S, O, Cl
O N
Nd
H2O Cl
Cl
H2O
(a)
O
OH2
Nd
OH2
S
S
(b)
Fig. 1. (a) Tentative structure of complex 2 with plausible ligancy 6. (b) Tentative structure of complex 5 with plausible ligancy 7. (c) Tentative
structure of complex 10 with plausible ligancy 9.
and Nd) data are in according with stoichiometry
proposed. The analytical and physical details are given
in Table 1(a) and 1(b).
4.1. FTIR spectral analysis
The infrared spectral data of these newly synthesized
neodymium(III) complexes show bands in the regions
3405e3380, 1662e1612, 476e450, 404e370,
355e328, 310e318 cm
1 which are assigned to n(NeH),
n(C]N), n(LneO), n(LneN), n(LneS) and n(LneCl)
respectively [44e55]. These data are summarized in
Table 2. Due to presence of water molecule in the com-
plexes, a broad band is present at 3440e3410 cm
1 which
could be assigned as n(OeH) [56]. The presence of water
molecule in these complexes is also confirmed by TG-
DTG decomposition curves. The calculated force con-
stant data reveals that the complexes 1e4 have lower
value of k, whereas the value of k are found to be
comparatively higher for mixed ligand complex 5e12.
The calculated force constants are also given in Table 2.
These values of k prompted that the neodymium-
pyrazoline complexes are comparatively less stable than
the mixed ligand neodymium complexes. This statement
is supported by the given absorption study.
OCH3
.H2O O N
OH2 NH .H2O
OCH3 Nd H2O
Cl
N OH2 H2O
H S S
O
(c)
H
N
N
H
Cl
 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273 261

4.2. DART mass spectrometry

Nd found (calc.)

(28.48)
(26.89)
(27.71)
(26.67)
(23.99)
(22.85)
(23.44)
(22.69)
(22.96)
(21.91)
(22.46)
(21.77)
The molecular ion peaks obtained by the DART
mass spectrometry, confirm the molecular weight of

28.35
26.72
27.64
26.73
23.89
22.71
23.41
22.60
22.39
21.82
22.37
21.88
the complexes. The peak at m/z ¼ 535.59 (2), 602.36
(5) and 660.74 (10) in the DART mass spectrum

12.60 (12.64)
14.95 (14.91)
12.28 (12.30)
11.80 (11.83)

10.11 (10.14)

17.62 (17.83)
19.33 (19.44)
17.37 (17.44)
16.85 (16.90)
pattern confirms their existence as monomer

8.01 (7.98)

7.82 (7.80)
7.56 (7.55)
[supporting information 1]. The fragmentation pattern

O found
(calc.)
of these neodymium complexes are also supported by
the TG-DTG decomposition pattern. All the fragments
of complexes are given in Table 3.

14.06 (14.00)
13.27 (13.22)
13.66 (13.62)
19.61 (19.66)

11.12 (11.15)

10.63 (10.70)
5.87 (5.90)
5.60 (5.62)
5.74 (5.76)

5.67 (5.64)
5.42 (5.39)
5.50 (5.52)
4.3. Thermogravimetric analysis

Cl found
(calc.)
The decomposition pattern of neodymium com-
plexes with respect to temperature was studied by the
TG-DTG analysis in the temperature range

10.63 (10.67)
10.13 (10.16)
10.44 (10.42)
10.12 (10.09)
10.34 (10.21)
39e720  C. The TG-DTG curve obtained by the py-

9.69 (9.74)
9.95 (9.98)
9.66 (9.68)
S found
rolysis of neodymium complexes reveals the presence

(calc.)
of water in all the complexes. The first weight loss in

e
e
e
e
complex 1e4 and 9e12 are seen around 98  C which
indicates the presence of crystallized water [57,58]
(5.53)
(5.22)
(5.38)
(5.18)
(6.99)
(6.66)
(6.83)
(6.61)
(4.46)
(4.26)
(4.36)
(4.23)
molecule outside the coordination sphere. There is no
N found
(calc.)

such weight loss indication in complex 5e8 which

5.56
5.25
5.36
5.15
7.04
6.69
6.80
6.63
4.48
4.29
4.33
4.21
infer to lack of crystallized water in these complexes.
The loss of coordinated water from all the complexes
(3.78)
(3.95)
(4.07)
(3.35)
(4.53)
(4.63)
(4.75)
(4.12)
(4.49)
(4.59)
(4.71)
(4.11)
can be seen by the presence of a broad peak in the
H found

temperature range 180e207  C in DTG curve. Pres-

(calc.)
3.80
3.93
4.05
3.33
4.50
4.61
4.73
4.09
4.42
4.57
4.69
4.09
ence of water is also supported by the FTIR spectral
analysis.
In complex 9e12, the sulfur containing organic
(35.57)
(35.82)
(36.92)
(33.31)
(39.95)
(39.95)
(40.99)
(37.79)
(34.41)
(34.67)
(35.53)
moiety was decomposed from anhydrous complexes (32.62)
C found

at temperature around 310  C whereas, in complex

(calc.)
35.62
35.95
37.09
33.46
40.11
40.10
41.13
37.87
35.00
34.84
35.72
32.46

5e8, this moiety is eliminated at around 421  C. The

reason of the temperature difference could be the
steric hindrance present in complexes 9e10 causing
[Nd(C2H5OCS2)(C15H12N2OCl)(4H2O)Cl]$H2O
[Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O
[Nd(C2H5OCS2)(C15H13N2O)(4H2O)Cl]$H2O

[Nd(C2H5OCS2)(C16H15N2O)(4H2O)Cl]$H2O

the loss of sulfur containing molecule at lower

temperature. Loss of pyrazoline moiety occurred in
[Nd(C5H10NS2)(C15H12N2OCl)(2H2O)Cl]
[Nd(C5H10NS2)(C16H15N2O2)(2H2O)Cl]
[Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl]

[Nd(C5H10NS2)(C16H15N2O)(2H2O)Cl]

the last step of decomposition which leads to the

[Nd(C15H12N2OCl)(2H2O)Cl2]$H2O
[Nd(C16H15N2O2)(2H2O)Cl2]$H2O

formation of Nd2O3. Pyrazoline decomposed at tem-

[Nd(C15H13N2O)(2H2O)Cl2]$H2O

[Nd(C16H15N2O)(2H2O)Cl2]$H2O

perature above 600  C due to the high bond dissoci-

Elemental analysis data of the complexes.

ation energy difference between the metaleoxygen

bond. The decomposition pattern of one of these
neodymium complexes is given in Fig. 2, in which
it is clearly seen that in complex 2, 54% weight
loss occurred at the temperature around 720  C,
Complex

whereas, in complex 5 and 10, 50% and 60% weight

loss are observed. This leads to the information that
the mixed ligand complexes of the type
[Nd(C5H10NS2)(C15H12N2OX)(2H2O)Cl] are more
Table 1a

Comp.

stable at higher temperature than the rest two types of

No.

10
11
12

neodymium complexes. This statement is

1
2
3
4
5
6
7
8
9
262 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273

Table 1b
Physical characterization data of the complexes.
Comp. No. Complex Yield Decomposition Mol. wt. found Physical state/Color
(%) point ( C) (calcd.)
1 [Nd(C15H13N2O)(2H2O)Cl2]$H2O 89 181 507.65 (506.47) Amorphous/Greenish-brown
2 [Nd(C16H15N2O2)(2H2O)Cl2]$H2O 82 182 535.59 (536.49) Amorphous/Greenish-brown
3 [Nd(C16H15N2O)(2H2O)Cl2]$H2O 87 182 521.63 (520.49) Amorphous/Greenish-brown
4 [Nd(C15H12N2OCl)(2H2O)Cl2]$H2O 79 183 542.66 (540.91) Amorphous/Greenish-brown
5 [Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl] 77 217 602.36 (601.27) Amorphous/Brownish-green
6 [Nd(C5H10NS2)(C16H15N2O2)(2H2O)Cl] 83 220 632.72 (631.29) Amorphous/Brownish-green
7 [Nd(C5H10NS2)(C16H15N2O)(2H2O)Cl] 76 219 616.39 (615.30) Amorphous/Brownish-green
8 [Nd(C5H10NS2)(C15H12N2OCl)(2H2O)Cl] 85 218 636.99 (635.71) Amorphous/Brownish-green
9 [Nd(C2H5OCS2)(C15H13N2O)(4H2O)Cl]$H2O 91 204 630.36 (628.25) Amorphous/Soil color
10 [Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O 89 206 660.74 (658.27) Amorphous/Soil color
11 [Nd(C2H5OCS2)(C16H15N2O)(4H2O)Cl]$H2O 83 205 644.78 (642.27) Amorphous/Soil color
12 [Nd(C2H5OCS2)(C15H12N2OCl)(4H2O)Cl]$H2O 86 205 665.13 (662.69) Amorphous/Soil color

Table 2
FTIR spectral data of the complexes.
Comp. Complex n (OeH) n n n (OeH) n n n n k  104

1
1
no. cm (NeH) (C]N) cm (NdeO) (NdeN) (NdeS) (NdeCl) (J/m2)
(coord.) cm
1 cm
1 (lattice) cm
1 cm
1 cm
1 cm
1
1 [Nd(C15H13N2O)(2H2O)Cl2]$H2O 3432 3400 1643 1620 453 370 e 312 1.8564
2 [Nd(C16H15N2O2)(2H2O)Cl2]$H2O 3436 3399 1640 1622 451 376 e 313 1.8401
3 [Nd(C16H15N2O)(2H2O)Cl2]$H2O 3430 3401 1639 1621 450 375 e 312 1.8319
4 [Nd(C15H12N2OCl)(2H2O)Cl2]$H2O 3440 3405 1636 1623 452 372 e 314 1.8483
5 [Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl] 3410 3398 1641 e 476 404 354 310 2.0498
6 [Nd(C5H10NS2)(C16H15N2O2)(2H2O)Cl] 3416 3389 1635 e 470 402 355 311 1.9984
7 [Nd(C5H10NS2)(C16H15N2O)(2H2O)Cl] 3412 3392 1652 e 467 397 352 311 1.9730
8 [Nd(C5H10NS2)(C15H12N2OCl)(2H2O)Cl] 3417 3396 1639 e 474 399 350 312 2.0326
9 [Nd(C2H5OCS2)(C15H13N2O)(4H2O)Cl]$H2O 3430 3392 1656 1626 468 383 329 315 1.9815
10 [Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O 3428 3380 1652 1627 465 380 332 317 1.9561
11 [Nd(C2H5OCS2)(C16H15N2O)(4H2O)Cl]$H2O 3434 3388 1640 1626 463 381 331 316 1.9393
12 [Nd(C2H5OCS2)(C15H12N2OCl)(4H2O)Cl]$H2O 3431 3394 1637 1625 462 386 328 318 1.9309

Table 3
DART mass fragmentation pattern of complexes.
Comp. no. Complex Mol. wt. found -H2O (lattice -H2O -Cl -Dtc -Xan -Py
(calcd.) water) (coord.)
1 [Nd(C15H13N2O)(2H2O)Cl2]$H2O 507.65 (506.47) 489.54 453.16 384.22 e e 144.39
2 [Nd(C16H15N2O2)(2H2O)Cl2]$H2O 535.39 (536.49) 520.01 482.19 410.33 e e 144.64
3 [Nd(C16H15N2O)(2H2O)Cl2]$H2O 521.63 (520.49) 503.76 464.65 395.88 e e 144.37
4 [Nd(C15H12N2OCl)(2H2O)Cl2]$H2O 542.66 (540.91) 524.12 488.23 416.25 e e 144.45
5 [Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl] 602.36 (601.27) e 568.56 528.75 380.23 e 144.96
6 [Nd(C5H10NS2)(C16H15N2O2)(2H2O)Cl] 632.72 (631.29) e 596.26 558.23 410.11 e 144.85
7 [Nd(C5H10NS2)(C16H15N2O)(2H2O)Cl] 616.39 (615.30) e 578.36 542.82 394.65 e 144.62
8 [Nd(C5H10NS2)(C15H12N2OCl)(2H2O)Cl] 636.99 (635.71) e 598.36 566.23 416.22 e 144.73
9 [Nd(C2H5OCS2)(C15H13N2O)(4H2O)Cl]$H2O 630.36 (628.25) 611.11 504.23 576.02 e 383.26 144.92
10 [Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O 660.74 (658.27) 642.00 534.16 605.96 e 413.31 144.79
11 [Nd(C2H5OCS2)(C16H15N2O)(4H2O)Cl]$H2O 644.78 (642.27) 626.37 518.79 590.17 e 396.84 144.86
12 [Nd(C2H5OCS2)(C15H12N2OCl)(4H2O)Cl]$H2O 665.13 (662.69) 647.63 540.00 612.14 e 418.36 144.90

also supported by the high decomposition temperature 4.4. Absorption spectral studies
of these neodymium complexes as shown in
Table 1(b). The decomposition patterns are given in The absorption spectral peaks of neodymium com-
Table 4. plexes were recorded in dichloromethane at room
 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273
Fig. 2. TG-DTG curve of complex 2.
temperature. To observe the effect of aging of com-
plexes on absorption of light and the nephelauxetic
effect [59], the sample was analyzed twice; once at the
time it prepared and once after nine months of syn-
thesis. A detailed study about the effect of aging and
the change of environment around the central metal
atom are discussed here. In the present manuscript, to
study the bonding characteristics of the metal and
ligand, the nephelauxetic parameter (b), parameter of
covalency (d), bonding parameter (b1/2), angular
covalency (h), relative nephelauxetic effect (db) and
the stabilization of the lowest subshell of the ground
level in the complex were calculated.
The absorption spectral study of the complexes in-
dicates the presence of LMCT and MLCT peaks pre-
sent at 30488 and 26455 cm
1 (2), 30674 and
26810 cm
1 (5) and 31348, 30960 and 30675 cm
1
(10) [60e62]. Red shift in the peaks with respect to
metal aquo ion confirms the formation of M-L com-
plex. These charge transfer peaks are of high intensity
in comparison to fef transition peaks. This is due to
the laporte allowed transition for the charge transfer
peaks [63,64].
In complex 2, beside the charge transfer peaks, four
fef transition peaks were seen as shown in Fig. 3(a).
These peaks are present at 17064, 13227, 12285 and
11337 cm
1 in fresh complex, whereas same peaks are
found somewhat higher wavenumber at 18018, 13550,
12610 and 11737 cm
1. These peaks resembles the
transitions from 4I9/2 ground level to 4G5/2, 4F7/2, 4F5/2,
4
F3/2 excited level of neodymium [65e69]. The
nephelauxetic effect is clearly seen in fresh complex,
whereas after few months, there is no such effect was
seen. The nephelauxetic ratio of fresh complex is
0.9819, whereas in aged complexes it is calculated as
1.0168. As given in literature [64,68], the parameter of
covalency was calculated from this nephelauxetic ratio.
263
The covalency of fresh complex is found to be 1.8385
which can be attributed as comparatively strong co-
valent bonding between metal and ligand [70]. The
positive b1/2 value indicates the involvement of 4f
orbital in metal ligand bonding [66]. The angular
covalency is found 0.1355. Slope of the graph between
Dn verses naquo are found 0.0215 indicates the decrease
of nephelauxetic ratio with respect to aquo ion [71],
whereas the intercept value represents the stabilization
of lowest sublevel of the complex. The stabilization of
the lowest subshell is found
45.7129 which is much
higher than the neodymium ion of free lowest subshell
[71].
The aging effect on complex 2 can be clearly seen
by the negative value of covalency parameter (d) which
indicates the change of covalent bond to ionic bond
[70]. The negative value of db (slope) indicates that
there is no nephelauxetic effect is seen in aged com-
plexes. A very high intercept value indicates very high
stable lowest subshell of neodymium. The calculated
zero value of bonding parameter (b1/2) also indicates
that there is no involvement of 4f orbital in metal
ligand bonding.
In fresh complex 5 and 10, there is strong neph-
elauxetic effect are seen in fef transition in compari-
son to free neodymium ion [71]. Both the complexes
show the transition from lower 4I9/2 level to 4G9/2, 4G5/
4 4 4
2, F7/2, F5/2 and F3/2 excited level of the neodymium.
Both the fresh complexes 5 and 10 have almost similar
value of covalency of bonding (d), nephelauxetic ratio
(b), involvement of 4f orbital, bonding parameter (b1/
2
), angular covalency (h), decrease in nephelauxetic
ratio (db) and the stability of lower subshell. The sta-
bility of lower subshell are found approximately

400 cm
1 cannot be acceptable because aquo ion has
itself
179 cm
1 value of lowest sub level [71,72].
These calculations reveal that in these complexes
neodymium form very strong covalent bond by having
the covalent bonding parameter approximately 2%.
On aging, there are some changes occur like the
transition from 4I9/2-4G5/2 disappeared in complex 5
and 10. The nephelauxetic effect is seen only in the 4I9/
2- G9/2 peak in complex 5 and in I9/2- G9/2 & I9/2- F5/
4 4 4 4 4
2 transitions in complex 6. Rest of the peaks does not
show such effect. All these peaks are shown in Fig. 3.
The calculation of parameter of covalency reveals that
on aging, there is some decrease in covalent character
of these complexes, but positive value of d reveals that
these complexes still have covalent character. This
covalent character is weak in complex 5, whereas this
is stronger in complex 10. The d, b1/2 and h value of
264 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273

Table 4
Decomposition pattern of the complexes obtained by the TG-DTG curves.
Comp. no. Complex Temperature ( C) Weight loss found (calcd.) Fragment lost
1 [Nd(C15H13N2O)(2H2O)Cl2]$H2O 97.36 4.00 (3.55) -H2O
180.00 7.12 (7.10) -2H2O
364.24 14.52 (14.01) -2Cl
624.55 46.21 (46.84) -C15H13N2O
2 [Nd(C16H15N2O2)(2H2O)Cl2]$H2O 97.90 2.00 (3.35) -H2O
185.72 7.63 (6.71) -2H2O
347.80 14.00 (13.23) -2Cl
634.42 50.66 (49.82) -C16H15N2O2
3 [Nd(C16H15N2O)(2H2O)Cl2]$H2O 98.21 2.99 (3.45) -H2O
186.33 6.31 (6.91) -2H2O
362.23 13.00 (13.64) -2Cl
662.32 47.12 (48.28) -C16H15N2O
4 [Nd(C15H12N2OCl)(2H2O)Cl2]$H2O 97.56 3.00 (3.32) -H2O
188.36 6.92 (6.65) -2H2O
367.67 12.56 (13.12) -2Cl
684.23 51.44 (50.23) -C15H12N2OCl
5 [Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl] 204.14 6.00 (5.90) -Cl
205.12 6.04 (5.98) -2H2O
420.10 24.82 (24.65) -C5H10NS2
602.44 39.33 (39.46) -C15H13N2O
6 [Nd(C5H10NS2)(C16H15N2O2)(2H2O)Cl] 202.74 5.80 (5.62) -Cl
203.14 5.82 (5.70) -2H2O
422.09 23.01 (23.44) -C5H10NS2
635.55 42.59 (42.34) -C16H15N2O2
7 [Nd(C5H10NS2)(C16H15N2O)(2H2O)Cl] 205.47 5.89 (5.76) -Cl
206.02 6.00 (5.85) -2H2O
422.65 24.56 (24.05) -C5H10NS2
615.78 41.08 (40.84) -C16H15N2O
8 [Nd(C5H10NS2)(C15H12N2OCl)(2H2O)Cl] 202.94 5.51 (5.58) -Cl
203.67 5.60 (5.66) -2H2O
421.24 23.91 (23.28) -C5H10NS2
633.65 42.12 (42.74) -C15H12N2OCl
9 [Nd(C2H5OCS2)(C15H13N2O)(4H2O)Cl]$H2O 98.82 2.69 (2.86) -H2O
160.63 5.34 (5.52) -Cl
204.38 10.98 (11.46) -4H2O
312.02 18.67 (19.29) -C2H5OCS2
631.29 36.11 (37.76) -C15H13N2O
10 [Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O 99.01 2.39 (2.73) -H2O
161.18 5.21 (5.39) -Cl
205.14 10.02 (10.93) -4H2O
311.45 17.80 (18.41) -C2H5OCS2
630.37 38.92 (40.60) -C16H15N2O2
11 [Nd(C2H5OCS2)(C16H15N2O)(4H2O)Cl]$H2O 99.39 2.61 (2.80) -H2O
160.23 5.46 (5.52) -Cl
205.93 10.92 (11.21) -4H2O
310.82 17.95 (18.87) -C2H5OCS2
632.11 38.37 (39.12) -C16H15N2O
12 [Nd(C2H5OCS2)(C15H12N2OCl)(4H2O)Cl]$H2O 99.51 2.42 (2.71) -H2O
159.98 5.29 (5.35) -Cl
204.44 10.22 (10.86) -4H2O
309.94 18.10 (18.29) -C2H5OCS2
631.78 38.84 (41.00) -C15H12N2OCl

fresh and aged complexes do not have much differ- The difference in the number of water molecules pre-
ences in itself which indicates that there is very less sent in the coordination sphere of complex 5 and 10
aging effect on complex 10. This might be due to the could be another reason for the less aging effect of
electronegativity difference of nitrogen and oxygen. complex 10 as compared to complex 5.
 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273
Fig. 3. (a) Absorption spectra of fresh and aged complex 2. (b)
Absorption spectra of fresh and aged complex 5. (c) Absorption
spectra of fresh and aged complex 10.
On comparison of all these three types of com-
plexes, it can be seen that the complex 2 have moderate
covalent bonding character in itself which on aging
changed to the ionic character and the involvement of
4f orbitals are zero, whereas complex 5 and 10 have
comparatively strong covalent character in both fresh
and aged conditions. Here, the reason could be the
presence of sulfur donor ligands in complex 5 and 10,
which increases the covalent character of the
metaleligand bonds. The relative nephelauxetic effects
265
are found quite higher in mixed ligand complexes in
comparison to the complex 2. Aging effects in mixed
ligand complexes are comparatively lower than the
simple neodymium-pyrazoline complexes which indi-
cate that the mixed ligand complexes are more stable
with respect to time. All the bonding characteristic and
parameter details are presented in Table 5.
4.5. Photoluminescence study
The photoluminescence investigation of these newly
synthesized complexes was executed by the electronic
absorption and emission spectra. The absorption
examine is presented above in detail. The emission
studies were carried out in dichloromethane media. To
study the emission phenomenon of neodymium com-
plexes, we are taking here few representative examples
of each type of complex, i.e. we are discussing here the
neodymium emission in complex 2, 5 and 10. The fef
transition due to neodymium is clearly seen in Fig. 4
Difference in the peak position is due to difference in
the environment around the neodymium. From the
given Fig. 4, it can be seen that there is a strong
emission peak observed at wavelength 366 (2), 365 (5)
and 370 (10) nm in all these three types of complexes.
These peaks are resembled to emission of purple light
from excited state 3P3/2 to 4I9/2 ground state [73]. Low
intensity peak present in 447e449 nm range of
wavelength, indicates the transition of electrons from
2
P1/2-4I9/2 state [74]. A comparatively stronger peak
present at 467 nm in all the complexes infer the blue
light emission caused by the transition from 4G11/2-4I9/
2 [74]. Another low intensity peak at 529 (2), 526 (5)
and 534 (10) could be assigning as the 4G7/2-4I9/2
transition, leads to the emission of green light
[73,75e77]. At wavelength 640 nm, a strong peak of
very high intensity is observed in complex 2 which
resembles to red light emission caused by the transition
of electrons from 2H11/2 to 4I9/2 [73,74]. The nature of
the emission peak in complex 5 and 10 are quite
similar due to almost same environment around the
central metal neodymium.
The quantum yields of these neodymium complexes
were calculated by the absorption and emission spec-
tral peaks [Table 6]. From the given Table 6, it is
shown that all these complexes absorb light at higher
wavelength in comparison to their respective ligands,
whereas, these complexes emits light at comparatively
lower wavelength, leads to high quantum yield of the
complexes than the ligands. Transition in ligands
usually occurred due to p-p* or n-p* electron transfer
within the molecule [57,78,79], whereas in neodymium
266 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273

Table 5a
Electronic parameters for complex 2.
S. no. Levels n (aquo) n (comp.) n (comp.) Dn Dn d (fresh) d (aged) Slope Slope
cm
1 fresh aged fresh aged Intercept (fresh) Intercept (aged)
1 4
G5/2 17380 17064 18018 316
638 1.8385
1.6548
2 4
F7/2 13510 13227 13550 283
40 0.0215
0.0864
3 4
F5/2 12500 12285 12610 215
110
4 4
F3/2 11520 11337 11737 183
217
45.7129 934.5269

Table 5b
Electronic parameters for complex 5.
S. no. Levels n (aquo) n (comp.) n (comp.) Dn Dn d (fresh) d (aged) Slope Slope
cm
1 fresh aged fresh aged Intercept (fresh) Intercept (aged)
4
1 G9/2 19570 18939 17986 631 1584 2.0042 1.1687
2 4
G5/2 17380 17069 e 311 e 0.0506 0.2348
3 4
F7/2 13510 13227 13605 283
95
4 4
F5/2 12500 12345 12626 155
126
444.449
3061.937
5 4
F3/2 11520 11350 11723 170
203

Table 5c
Electronic parameters for complex 10.
S. no. Levels n(aquo) n (comp.) n (comp.) Dn Dn d (fresh) d (aged) Slope Slope
cm
1 fresh aged fresh aged Intercept (fresh) Intercept (aged)
4
1 G9/2 19570 18903 18018 667 1552 2.0882 1.7558
2 4
G5/2 17380 17064 e 316 e 0.0520 0.2140
3 4
F7/2 13510 13262 13623 248
113
4 4
F5/2 12500 12330 12422 170 78
453.206
2699.515
5 4
F3/2 11520 11312 11614 208
94

Table 5d
Bonding parameters for complex 2, 5 and 10.
Large stoke shift in the ligands is due to the emis-
1/2 1/2
sion from intramolecular charge transfer (ICT). The
Comp. bav bav b b h h
No. (fresh) (aged) (fresh) (aged) (fresh) (aged)
pyrazolines show fluorescence property itself due to
this intramolecular energy transfer, in which one part
2 0.9819 1.0168 0.0672 0 0.1356 0
5 0.9804 0.9884 0.0701 0.0537 0.1416 0.1081
of the molecule act as donor, absorb light and another
10 0.9795 0.9827 0.0715 0.0657 0.1445 0.1325 part of the same molecule act as an acceptor, which
emits light [85e92]. Small stoke shift in the neo-
complexes these phenomenon occurred due to fef dymium complexes reveals that there is no such ICT
transition. found here rather the transfer of charge occurred due to
From the given Table 6, it is clearly seen that all the the intermolecular energy transfer between metal and
neodymium complexes show enhanced quantum yield ligand. Small stoke shift also indicates that there is
in comparison to their respective ligands. Pyrazolines pure vibrational shift occurred in these neodymium
are known to have luminescence property in itself; complexes.
therefore it is mark effect to observe the effect of Fluorescence life time analyses were carried out in
complex formation on quantum yield. Due to forbidden dichloromethane at room temperature, showing the
fef transition, the neodymium is incapable to sensitize single exponential decay in these neodymium com-
itself [80e83], therefore, to sensitize them a sensitizer plexes [Supporting information 2]. From fluorescence
[an organic moiety] was introduced. The pyrazoline is life time decay curve and quantum yield, radiative
an organic moiety which acts as sensitizer and sensi- decay rate (Kr) and non-radiative decay rate (Knr)
tizes the neodymium on account of having the similar were calculated. All these values are given in Table 6.
energy of its triplet state with lowest excited level of From the given table it can be seen that all these
neodymium [12,13,84]. complexes have high radiative decay rate and
 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273 267

comparatively much lower non-radiative decay rate,

indicating that most of the energy released is in form
of light and a very less amount of energy liberates as
heat. High quantum yield, with respect to dyes [93],
comparatively high fluorescence life time, high radi-
ative decay rate and much lower non-radiative decay
rate make these newly synthesized materials more
commercially valuable.

4.6. Determination of particle/crystallite size by

PXRD, TEM and SEM methods

The powder X-ray diffraction of these newly syn-

Fig. 4. (a) Emission spectra of complex 2. (b) Emission spectra of
complex 5. (c): Emission spectra of complex 10.
thesized complexes was carried out by Bruker AXS D8
Advance diffractometer. These complexes were
calcined up to 450  C to observe the particular
reflection peak caused by the crystalline complexes.
On calcination, weak reflection peaks were observed
indicating the amorphous nature of the complexes [34].
Lattice dynamics of these amorphous complexes of
neodymium were inferred by the help of peaks and
data obtained from the PXRD analysis. With the help
of these analysis data, the indexing was done by the
program EXPO2014 [94]. The indexing results indi-
cate that these neodymium complexes have cubic lat-
tice [36] with space group Pn-3n/P4132 (2), Fd-3m (5)
and P4132 (10). Miller indices corresponding to 2q
values, cell parameter (a), d-spacing value and lattice
strain were calculated by standard method [95] and
these all are given in Table 7(a) in which it can be seen
that the calculated lattice strain is having quite low
value indicating the less lattice dislocation aroused
from the crystal imperfection.
The powder X-ray diffraction peaks of these neo-
dymium complexes were compared by the Nd2O3
particles [96] to observe the shift in the characteristic
peak of neodymium. The characteristic peak of neo-
dymium is seen in the obtained PXRD pattern of the
neodymium complexes. There is slight change in their
2q position indicating the complex formation. All these

Table 6
Photoluminescence data of some representative complexes and their respective ligands.
Comp. no. Ligand/Complex Absorption Emission Stoke F Kr (106 s
1) Knr (106 s
1) t (ns)
(nm) (nm) shift (nm)
Pyrazoline (C15H13N2OH) 272 435 163 0.62 e e e
Methoxy-pyrazoline (C15H13N2O.OCH3) 300 474 174 0.63 e e e
Sodium diethyldithiocarabamate 264 403 139 0.65 e e e
Potassium ethylxanthate 286 455 169 0.63 e e e
2 [Nd(C16H15N2O2)(2H2O)Cl2]$H2O 328 366 38 0.90 14.17 1.64 63.22
5 [Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl] 326 365 39 0.89 21.33 2.67 41.72
10 [Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O 319 370 51 0.86 24.83 4.04 34.64
268 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273

Table 7a
Structural characteristics of crystal system obtained by PXRD method.
Comp. Complex Peak no. 2q d (Å) sin2 q h2 þ k2 þ l2 hkl a Lattice Space group Crystal
no. strain system
2 [Nd(C16H15N2O2)(2H2O)Cl2]$H2O 1 26.82 3.32 0.054 3 111 5.75 0.0042 Pn-3n/P4132 Cubic
2 31.04 2.88 0.072 4 200 5.76 0.0056
3 35.39 2.53 0.092 5 210 5.66 0.0067
4 53.67 1.71 0.204 11 311 5.67 0.0027
5 [Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl] 1 26.92 3.31 0.054 3 111 5.73 0.0061 Fd-3m Cubic
2 31.00 2.88 0.071 4 200 5.76 0.0052
3 35.46 2.53 0.093 5 210 5.66 0.0051
4 40.63 2.22 0.125 6 211 5.44 0.0035
5 53.75 1.70 0.204 11 311 5.64 0.0025
10 [Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O 1 26.88 3.31 0.054 3 111 6.09 0.0054 P4132 Cubic
2 31.01 2.88 0.071 4 200 4.99 0.0051
3 37.65 2.39 0.104 6 211 4.78 0.0053
4 53.77 1.70 0.205 11 311 5.64 0.0025

Table 7b
Average crystallite/particle size obtained by *PXRD, #SEM and $TEM.
Comp. no. Complex Average crystallite Average diameter# Average diameter$
size* (nm) (mm) (nm)
2 [Nd(C16H15N2O2)(2H2O)Cl2]$H2O 29.72 3.21 10.90
5 [Nd(C5H10NS2)(C15H13N2O)(2H2O)Cl] 41.58 3.98 32.69
10 [Nd(C2H5OCS2)(C16H15N2O2)(4H2O)Cl]$H2O 61.05 4.29 45.45

three types of neodymium complexes are having the reason for differences in sizes obtained from the PXRD
characteristic peak at slight different 2q position also and TEM. From the TEM image, as given in Fig. 5, it is
indicate that there is change in environment around the clearly seen that complex 2 have some disc like shape in
central metal atom neodymium. Miller indices corre- itself, whereas there is no such clear shape are seen in
sponding to the 2q value 53.686, 53.755 and 53.769 are complex 5 and 10 [Supporting information 4]. The
311 [97,98]. Rest of the miller indices with respect to diffused ring pattern obtained in SAED pattern, given as
their 2q position were compared by the literature supporting information 5, indicates the amorphous na-
[86,88,89] and are given in Table 7(a) which are in ture of the neodymium complexes [103].
good agreement with literature present [supporting
information 3].
The average crystallite sizes were calculated by the
Scherer formula [99e102]. All these complexes having
crystallite size in nano range [Table 7(b)]. From Table
7(b), it can be seen that the particle/crystallite size ob-
tained from TEM images are quite closer but still
somewhat smaller than the average crystallite sizes
obtained by PXRD analysis. Since transmission electron
microscopic images are obtained from the transmission
of electron from the inner surface of the particle,
therefore the measurement we make is generally from
the inner core shell of the particle. This could be the
reason that the particle size obtained from the TEM is
somewhat lower than the sizes of crystallite obtained
from PXRD pattern. Since there are more than one peak
obtained in the powder X-ray diffraction pattern,
therefore by taking average, sizes might be slight
different from the original one and this could be another Fig. 5. TEM image of the nano sized complex 2.
 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273
Fig. 6. SEM image, showing the surface morphology of complex 5.
The surface morphology of these neodymium
complexes can be seen by the SEM image, an example
is given as Fig. 6. The complex 2 and 10 have no clear
surface morphology; in fact some irregular sizes and
shape of the particle aggregates were seen [Supporting
information 6]. Some irregular cubes like structure
were seen in these images but fail to clearly interpret
its surface structure. The complex 5 have irregular
size globular structure at its surface. The particle sizes
obtained from the SEM images are much higher than
the size obtained by the PXRD calculation and TEM
images. The reason behind this could be the inter-
molecular hydrogen bonding at the surface of the
complexes resulting in associated molecules of large
particle sizes [104]. The obtained average particle
sizes from different sources are given in Table 7(b).
5. Conclusions
The present study focuses on the synthesis, char-
acterization, structure determination, stability towards
time and temperature, and the fluorescent properties of
neodymium complexes. The XRD study reveals that all
these complexes have cubic crystallite system. XRD
and TEM studies show that all these particles are of
nano size. SEM pictures show the surface morphology.
FTIR spectroscopy indicates the bidentate mode of
bonding by ligand as well as the bonding between
metal and heteroatoms. Presence of water molecules
and molecular weight were confirmed by TG-DTG
analysis. Monomeric nature of the complexes was
suggested by the DART mass spectrometry and
elemental analysis. This article unveils that through
TG-DTG, the complexes of type [Nd(C5H10NS2)
(C15H12N2OX)(2H2O)Cl] are more stable towards the
temperature in comparison to the rest two types of
complexes. The aging effect was studied by the
269
absorption spectra, which revealed that there is less
effect of aging on mixed ligand complexes than the
complexes having only one type of ligand, like
[Nd(C15H12N2OX)(2H2O)Cl2]$H2O. Therefore one can
say that these mixed ligand complexes of neodymium
can be used after a long time after its synthesis. The
photophysical studies reveals that these neodymium
complexes having much greater fluorescent property,
might be used as blue, violet, green or red light emitters.
Enhanced quantum yield than the reported dyes like
cresyl violet (0.578), oxazine 170 (0.579), oxazine 1
(0.141), cryptocyanine (0.012), HITCI (0.283), IR-125
(0.132), IR-140 (0.167) etc., make it more useful for
commercial purpose.
From the present study following points can also be
concluded:
➢ Complex 1e4 signify high quantum yield, radiative
decay rate and life time.
➢ Complex 5e8 signify moderate quantum yield,
radiative decay rate and life time.
➢ Complex 9e12 signify lowest quantum yield,
radiative decay rate and life time.
➢ The aging effect was highest on complex 1e4,
whereas complex 5e12 show very less aging effect.
➢ Shelf-life of the complex 5e12 is much higher than
the complex 1e4.
Conflict of interest
None.
Acknowledgments
The authors are grateful to SAIF, CDRI, Lucknow,
India, SAIF, IIT Madras, India, STIC, Cochin, India for
providing the necessary spectral and analytical data.
This work is financially supported by UGC-BSR pro-
gram [F. No. 25-1/2014-15/(BSR)/5-25/2007(BSR)].
We are also thankful to department of Chemistry, D. D.
U. Gorakhpur University, Gorakhpur, India for
providing the laboratory and library facilities.
Abbreviations
Na[C5H10NS2]$3H2O Sodium diethyldithiocarbamate
ligand (Dtc).
K[C2H5OCS2] Potassium ethylxanthate ligand (Xan).
270 I. Ameen et al. / Karbala International Journal of Modern Science 4 (2018) 258e273
C15H13N2OX (where, X ¼ H, OCH3, CH3, Cl) 3(2-
hydroxyphenyl)-5-(4-substituted phenyl) pyr-
azoline ligand (Py).
[Nd(C15H12N2OX)(2H2O)Cl2]$H2O Neodymium-pyr-
azoline complex
[Nd(C5H10NS2)(C15H12N2OX)(2H2O)Cl]
Neodymium-pyr-
azoline-diethyldithiocarbamate complex
[Nd(C2H5OCS2)(C15H12N2OX)(4H2O)Cl]$H2O
Neodymium-pyrazoline-ethylxanthate
complex
Appendix A. Supplementary data
Supplementary data related to this article can be
found at https://doi.org/10.1016/j.kijoms.2018.05.001.
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