Full text of DOI:10.1016/j.molstruc.2017.08.074

Accepted Manuscript
Cu(II) and Ni(II) 4-cyanobenzoate complexes with nicotinamide: Synthesis, spectral,
structural and optical characterization and thermal behavior
Füreya Elif Özbek, Mustafa Sertçelik, Mustafa Yüksek, Hacali Necefoğlu, Raziye
Çatak Çelik, Gamze Yılmaz Nayir, Tuncer Hökelek
PII:
S0022-2860(17)31143-2
10.1016/j.molstruc.2017.08.074
MOLSTR 24212
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 1 August 2017
Revised Date: 18 August 2017
Accepted Date: 22 August 2017
Please cite this article as: Fü.Elif. Özbek, M. Sertçelik, M. Yüksek, H. Necefoğlu, Raziye.Ç. Çelik,
Gamze.Yı. Nayir, T. Hökelek, Cu(II) and Ni(II) 4-cyanobenzoate complexes with nicotinamide: Synthesis,
spectral, structural and optical characterization and thermal behavior, Journal of Molecular Structure
(2017), doi: 10.1016/j.molstruc.2017.08.074.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Cu(II) and Ni(II) 4-Cyanobenzoate Complexes with Nicotinamide: Synthesis, Spectral,
Structural and Optical Characterization and Thermal Behavior
a*
a
b
c,d
e
Füreya Elif Özbek , Mustafa Sertçelik , Mustafa Yüksek , Hacali Necefoğlu , Raziye Çatak Çelik Gamze
c
f
Yılmaz Nayir , Tuncer Hökelek
a
Kafkas University, Department of Chemical Engineering, Faculty of Engineering and Architecture, 36300
Kars, Turkey.
b
Kafkas University, Department of Electrical and Electronics Engineering, Faculty of Engineering and
Architecture, 36300 Kars, Turkey.
c
Kafkas University, Department of Chemistry, Faculty of Sciences and Arts, 36300 Kars, Turkey.
d
International Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan.
e
Scientific and Technological Application and Research Center, Aksaray University, 68100 Aksaray, Turkey.
f
Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey,
*
Corresponding author: fozturkkan36@gmail.com (Füreya Elif Özbek)
Abstract
Two new copper(II) and nickel(II) complexes [M(NC-C H COO) (C H N O) (H O) ] (where
6
4
2
6
6
2
2
2
2
M:Cu and Ni) have been synthesized and characterized by elemental analysis, FT-IR and UV-
Vis spectroscopy, spectroscopic ellipsometer (SE), X-ray crystallography, thermal analysis
and molar conductivity. X-ray measurements showed that both of the complexes crystallized
in triclinic system with the space group P-1. The isostructure complexes have distorted
octahedral geometry around the metal atom center. In both of the crystal structures, the metal
atoms are coordinated by two nitrogen atoms from two different nicotinamide ligands, two
carboxyl oxygen atoms from two different 4-cyanobenzoate anions and two oxygen atoms
from two different water molecules. From the linear absorption spectra and spectroscopic
ellipsometer measurements, it was observed that these complexes showed different optical
behaviors.
1

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Keywords: 4-Cyanobenzoic Acid, Cu(II), Ni(II), optical characterization, Nicotinamide,
XRD
1
. Introduction
Besides the cost effective synthesizing and intriguing variety of architectures depending on
central metals benzoic acid derivatives are desired and investigated candidates for gas storage,
ion exchange, bio-medical, luminescence, magnetic, electric properties and nonlinear optics
fields [1-8]. For instance, V. Natarajan et al. showed that ethyl p-aminobenzoate had six
times higher second harmonic generation (SHG) efficiency than that of potassium dihydrogen
phosphate (KDP) which is well known as nonlinear optical material [7]. Metal organic
frameworks (MOFs) are also suitable materials for use as functional materials in the above-
mentioned applications due to their structural variability [9-15]. Metal complexes of aromatic
carboxylic acids have a wide range in the literature due to their physical and biological
importance as well as different structural features. The complexes of 4-cyanobenzoic acid
which is one of aromatic carboxylic acids has two different functional coordination groups
exhibit structurally diversities and some physical properties due to the different ligand-metal
interactions. In the literature, there are many studies on 4-cyanobenzoic acid complexes [16-
2
1]. Over the last decade, the metal(II) arylcarboxylate complexes with ligands that
containing N- and O- donor atoms have also been extensively studied because of their
contributions to material science for discovering of different application fields [22-29].
Nicotinamide is also one of the N- and O- donor ligands that is usually act as a monodentate
ligand by using nitrogen atom as donor of pyridine ring and rarely act as a bidentate ligand
while uses both of oxygen and nitrogen atoms as donors of carbonyl group and pyridine ring,
respectively. There is no complex in the literature that coordinated only with oxygen atom
[
28, 30-31].
2

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To the best of our knowledge, the optical characteristics (linear refraction index, linear
absorption and extinction coefficients) of Cu(II) and Ni(II) arylcarboxylate complexes
(complex 1 and complex 2, respectively) haven’t been investigated in detail, yet. For this
reason, in this study we investigated the optical properties of synthesized complex 1 and
complex 2 by using UV-Vis spectrophotometer and spectroscopic ellipsometer (SE).
2
2
. Experimental
.1. Chemical reagents
The chemicals used were of reagent grade (Aldrich or Sigma) and used without further
purification.
2
2
.2. Synthesis of the complexes
.2.1. Synthesis of Diaquabis(4-cyanobenzoato-κO)bis(nicotinamide-κN')copper(II)
(
Complex 1)
To prepared sodium 4-cyanobenzoate salt, 0.84 g (10 mmol) of sodium bicarbonate and
.47 g (10 mmol) of 4-cyanobenzoic acid were mixed in 50 mL water and continiously
stirred at 60°C till removed of CO gase. In another beakers, CuSO .5H O 1.24g (5 mmol)
1
2
4
2
and nicotinamide 1.22 g (10 mmol) were dissolved 50 mL water. Nicotinamide solution and
sodium 4-cyanobenzoaate solution were added on CuSO .5H O solution, respectively. The
4
2
obtained clear solution was kept for crystallization at ambient atmosphere. After three weeks,
blue single crystals that were obtained for by slow evaporation of the solution were filtered
off, washed with water and dried at room temperature. Anal. Calcd. (%) for Complex 1,
[
(
Cu(NC-C H COO) (C H N O) (H O) ] (MW = 636.08) C, 52.87; H, 4.09; N, 13.20. Found
6 4 2 6 6 2 2 2 2
-1
%): C, 53.05; H, 3.80; N, 13.21; Selected IR bands (cm ): ν(OH)
3500, ν(NH )
3370,
H2O
2 arom.
ν(C-H)arom. 3185, ν(C=O)amide 1691, ν(C-N) 2230, νCOO-) 1585, ν(COO-) 13828, ꢀν(COO-
as
s
3

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-
)
[
197, ν(C-C)phen 1430, δ(COO ) 874, δ(C-H)phen. 750, ρr(H O), 783 ρw(H O) 652. UV–Vis
2
2
λ (nm),]: 450, 715. Molar Conductivity (µS/cm): 5.0.
2
.2.2. Synthesis of Diaquabis(4-cyanobenzoato-κO)bis(nicotinamide-κN')nickel(II)
(Complex 2)
The synthesis of Complex 2 was similar to that of Complex 1 except that NiSO .6H O (1.31
4
2
g, 5 mmol) was used instead of the CuSO .5H O. After two weeks, blue single crystals that
4
2
were obtained for by slow evaporation of the solution were filtered off, washed with water
and dried at room temperature. Anal. Calcd. (%) for Complex 2, [Ni(NC-
C H COO) (C H N O) (H O) ] (MW = 631.22) C, 53.28; H, 3.83; N, 13.31. Found (%): C,
6
4
2
6
6
2
2
2
2
-1
5
5.40; H, 3.56; N, 13.74; Selected IR bands (cm ): ν(OH)
3173, ν(NH )
3314, ν(C-
H2O
2 arom.
-
H)arom. 3185, ν(C=O)amide 1691, ν(C-N) 2230,
ν(COO-) 1585, ν(COO ) 13828,
as
s
-
ꢀ
ν(COO-) 197, ν(C-C)phen 1430, δ(COO ) 874, δ(C-H)phen. 750, ρr(H O), 783 ρw(H O) 652.
2
2
UV–Vis [λ (nm),]: 350, 646. Molar Conductivity (µS/cm): 8.1.
2
.3. Physical Measurements
Elemental analysis for C, H and N were performed by using a LECO, CHNS-932 elemental
analyzer. The thermogravimetry (TG) curves were collected with a ShimadzuTG-50 analyzer.
The thermal properties of the complexes were measured and recorded simultaneously with a
help of Schimadzu DTG 60 thermal analyzer. The experiments were carried out in static
-1
nitrogen atmosphere with a heating rate of 10ºC min from room temperature to 1000°C in
platinum crucibles. The samples were approximately 10 mg and highly sintered α-Al O was
2
3
-1
used as a reference material. The DTG sensitivity was 0.05 mg.s . Molar conductivity of the
-3
complexes were measured by using COND iSET315 in DMF (10 M) at room temperature.
TM
FT-IR Spectra were recorded on Perkin Elmer Frontier FT-IR Spectrometer with solid
4

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-1
samples using a Diamond ATR accessory in the range of 4000-600 cm . Resolution was set
−
1
up to 4 cm , signal/noise ratio was established by 4 scans.
2
.4. Crystallography
Single-crystal X-ray diffraction analyses of Complex 1 and 2 were performed on a Bruker
SMART BREEZE CCD diffractometer using Mo K (λ= 0.71073 Å) radiation at a
α
temperature of 296 K. Structures were solved by direct methods and refined by full-matrix
2
least squares against F using all data [32]. All non-H atoms were refined anisotropically.
Atoms H41 and H42 (for H O) (in Complex 1) and atoms H41, H42 (for H O) and H31, H32
2
2
(
for NH ) (in Complex 2) were located in difference Fourier maps and refined isotropically,
2
while the remaining H atoms were positioned geometrically at distances of 0.93 Å (aromatic
CH) (in Complex 1 and 2) and 0.86 Å (for NH ) (in Complex 1) from the parent C and N
2
atoms; a riding model was used during the refinement processes and the U (H) values were
iso
constrained to be 1.2U (carrier atom). Experimental data are given in Table 1.
eq
2
.5. Thin Film Deposition
For the fabrication of the thin films of all investigated complexes, 110 g/L solution of PMMA
in cyclohexanone was solved in a low power sonic bath for 48 h until completely dissolved.
The complex 1 and complex 2 were then added, and were also sonically agitated until they
were completely dissolved and a homogeneous solution was formed. Solid-state films of
samples were formed on quartz glass substrates by using a multilayer conventional spin
coating technique (SCS-Spin Coat G3P). Prepared films were baked for approximately 1 h at
5
5 °C to facilitate the removal of residual solvent.
5

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2
.6. UV-Vis and Spectroscopic Ellipsometer Experiments
The absorption spectra of the Complex 1 and Complex 2 films were acquired using a UV-Vis
absorption spectrophotometer (Shimadzu UV-1800) versus an uncoated glass substrate as
reference. SE uses to determine thicknesses and optical properties (linear refractive indices
(
n0) and extinction coefficients (k)) of thin films. Work principle of ellipsometer, depends on
measure the ratio of the complex Fresnel reflection coefficients, , where
= r r = tan Ψ exp i∆
ρ
ρ
(
)
.
(1)
p
s
Ψ and ∆ two parameters that are measured as angles, as result of the change of the
polarization state of an incident beam is determined in reflection or transmission from linear
to elliptical polarization.
SE experiments were carried out by using the instrument J.A. Woollam Co.-M2000V in the
photon energy range from 1.24 to 3.34 eV (from 370 to 999 nm). All the spectra were taken at
three angles of incidence (55°, 60° and 65°) to increase the fitting accuracy [33]. Optical
TM
modeling and data analysis were done using the Woollam Company WVASE32 software
package [34].
3
3
. Result and Discussion
.1. Descriptions of the crystal structures
The X-ray structural determinations of Complex 1 and 2 confirm the assignments of their
structures from spectroscopic data. Selected bond lengths and angles are given in Table 2.
Hydrogen bond geometry is given in Table 3. The molecular structures along with the atom-
numbering schemes are depicted in Figure 1 and Figure 2, while the packing diagrams are
given in Figure 3 and Figure 4, respectively.
6

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In the mononuclear complexes, the metal (Cu and Ni for Complex 1 and Complex 2,
respectively) atoms are located on inversion centres and coordinated by two 4-cyanobenzoate
(CNB) anions, two nicotinamide (NA) ligands and two water molecules, with all ligands
coordinating in a monodentate manner (Figs. 1 and 2). The two symmetry-related carboxylate
i
i
O atoms (O2 and O2 ) and the two symmetry-related water O atoms (O4 and O4 ) form
slightly distorted square-planar arrangements, while the slightly distorted octahedral
i
coordination spheres are completed by the two symmetry-related N atoms (N2 and N2 ) of the
two NA ligands in the axial positions [symmetry codes: (i) 1 – x, 1 – y, – z (for Complex 1)
and (i) – x, – y, – z (for Complex 2)]. In Complex 1, intramolecular O-H···O hydrogen bonds
(Table 3) link the water hydrogens to the carboxylate oxygens.
The very similar C1-O1 and C1-O2 bond lengths (Table 2) of the carboxylate groups indicate
delocalized bonding arrangements, rather than localized single and double bonds. The M-O
bond lengths (where M is metal) are 1.9830(16) Å (in Complex 1) and 2.0633(9) Å (in
Complex 2) (for benzoate oxygen atoms) and 2.4600(22) Å (in Complex 1) and 2.0955(9) Å
(in Complex 2) (for water oxygen atoms), and the M-N bond lengths are 2.0124(19) Å (in
Complex 1) and 2.0849(10) Å (in 2) (Table 2). The M atoms lie 0.4500(1) Å above (in
Complex 1) and 0.3866(1) Å below (in Complex 2) the planar (O1/C1/O2) carboxylate
groups. The O-M-O and O-M-N bond angles deviate only slightly from ideal values, with
average values of 90(8)° (in Complex 1) and 90(4)° (in Complex 2) and 90(8)° (in Complex
1
) and 90(4)° (in Complex 2), respectively (Table 2). The dihedral angles between the planar
carboxylate groups (O1/C1/O2) and the adjacent benzene rings [A (C2–C7)] are 20.71(21)°
in Complex 1) and 22.30(10)° (in Complex 2), while the benzene and pyridine [B (N2/C9–
(
C13)] rings are oriented at dihedral angles of 84.25(7)° (in 1) and 89.93(4)° (in Complex 2).
In the crystal structures of Complex 1 and 2, N-H···O (c = carboxylate), N-H···O (n =
c
n
nicotinamide) and O-H ···O (w = water) (for Complex 1) and N-H···O , N-H···O , O-
w
n
c
n
7

ACCEPTED MANUSCRIPT
H ···O and O-H ···O (for Complex 2) hydrogen bonds (Table 3) link the molecules,
w
n
w
c
2
4
enclosing R (8) and R (8) ring motifs [35], forming layers parallel to (001) (Figs. 3 and 4).
2
4
The layers are further linked via C-H ··· O (cnb = 4-cyanobenzoate) and C-H ···N
cnb
cnb
c
n
hydrogen bonds (Table 3), resulting in three-dimensional networks. The weak C-H···π
interactions are also observed (Table 3).
Figure 1. An ORTEP-3 [36] view of Complex 1. The thermal ellipsoids are drawn at the
5
0% probability level. Hydrogen bonds are shown as dashed lines.
Figure 2. An ORTEP-3 [36] view of Complex 2. The thermal ellipsoids are drawn at the
5
0% probability level.
8

ACCEPTED MANUSCRIPT
Figure 3. A partial packing diagram of Complex 1 viewed down [001], where b-axis is
horizontal and a-axis is vertical. Intermolecular N-H···O and O-H···O hydrogen bonds are
shown as dashed lines. Non-bonding H atoms have been omitted for clarity.
Figure 4. A partial packing diagram of Complex 2 viewed down[001], where b-axis is
horizontal and a-axis is vertical . Intermolecular N-H···O and O-H···O hydrogen bonds are
shown as dashed lines. Non-bonding H atoms have been omitted for clarity.
9

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Table 1. Experimental details for Complex 1 and 2.
Compound
Complex 1
Complex 2
Empirical Formula
Colour/shape
C H CuN O
C H NiN O
8
28
24
6
8
28 24
light translucent
blue/prism
6
translucent
blue/prism
light
Formula weight
Temperature (K)
636.08
296(2)
631.22
296(2)
Radiation, graphite
monochr.
Mo K (λ = 0.71073)
Mo K (λ = 0.71073)
α
α
Crystal system
Space group
a, b, c (Å),
triclinic
triclinic
P -1
P -1
7.7563(2), 9.8735(3), 7.6441(2),
9.8583(3),
84.042(3),
9
.9911(3)
10.2482(3)
α, β,ᵞ (°)
77.334(3), 84.430(4), 78.712(3),
7
4.894(3)
71.740(2)
1358.85(2)
1
3
Volume (Å )
720.07(4)
Z
1
-1
Abs. coefficients (mm )
0.819
0.736
-
3
Dcalc (mg m )
1.467
1.459
Max. crystal dim. (mm)
Θ(max) (°)
0.17X0.36X0.47
28.54
0.24X0.29X0.48
28.44
Reflections measured
Range of h, k, l
3599
3591
-10<h<10,-13<k<13,-
-10<h<10,-13<k<12,-
13<l<13
1
2<l<13
Diffractometer/scan
Bruker SMART BREEZE CCD / phi and w
3475
No of reflections with I>2 3145
σ(I)
Corrections applied
Lorentz polarization
Computer programs
Source of scatter. Factors
Structure solution
SHELXS-97, SHELXL-97, ORTEP-3 [32, 36]
International Table for X-Ray Crystallography [37]
Direct methods
Treatment of hydrogen
atoms
Geometric calculation and difference Fourier map
No of parameters varied
GOF
204
212
1.120
0.0469
0.1220
1.198
-0.346
1.058
0.0275
0.0763
0.298
-0.243
R = IIF I – IF II / IF I
o
c
o
Rw
-
3
(ꢀρ)max (e Å )
-3
(ꢀρ)min (e Å )
1
0

ACCEPTED MANUSCRIPT
Table 2. Selected bond lengths (Å) and angles (°) for 1 and 2.
1
2
Cu1-O2
Cu1-O4
Cu1-N2
O1-C1
O2-C1
O3-C14
N1-C8
1.9830(16)
2.4600(22)
2.0124(19)
1.239(3)
1.261(3)
1.230(3)
Ni1-O2
Ni1-O4
Ni1-N2
O1-C1
O2-C1
O3-C14
N1-C8
N3-C14
2.0633(9)
2.0955(9)
2.0849(10)
1.2557(16)
1.2547(15)
1.2356(17)
1.134(3)
1.131(5)
1.325 (3)
N3-C14
1.3207(18)
O2-Cu1-N2i
O2-Cu1-N2
O2-Cu1-O4i
O2-Cu1-O4
N2-Cu1-O4i
N2-Cu1-O4
O1-C1-O2
89.48(8)
90.52(8)
94.48(8)
85.52(8)
86.87(8)
93.13(8)
126.7(2)
O2-Ni1-N2
O2-Ni1-N2
O2-Ni1-O4
O2-Ni1-O4
N2-Ni1-O4
N2-Ni1-O4
O1-C1-O2
89.93(4)
90.07(4)
86.97(4)
93.03(4)
87.12(4)
92.88(4)
125.91(12)
ii
ii
ii
Symmetry codes: (i) 1 – x, 1 – y, – z, (ii) – x, – y, – z.
1
1

ACCEPTED MANUSCRIPT
o
Table 3. Hydrogen-bond geometry (
Å
, )
Compound D-HꢀꢀꢀA D-H
HꢀꢀꢀA
2.07
DꢀꢀꢀA
D-HꢀꢀꢀA
158
i
N3-H3A···O3 0.86
2.885 (3)
2.893 (3)
2.944 (3)
2.744 (3)
3.425 (4)
3.296 (6)
3.644 (3)
ii
N3-H3B···O1 0.86
2.16
143
iii
O4-H41···O3
O4-H42···O1
0.80(4)
0.88(5)
2.19(4)
1.89(5)
2.50
158(4)
162(5)
171
1
iv
C4-H4···O1
0.93
0.93
0.93
v
C9-H9···N1
2.56
136
vi
C6-H6···Cg2
2.72
175
i
N3-H31···O1
N3-H32···O3
O4-H41···O3
O4-H42···O1
0.85(2)
0.83(2)
0.79(2)
0.82(2)
0.93
2.141(19) 2.9038(19)
149.0(19)
165(2)
163(2)
163(2)
173
ii
iii
iv
2.11(2)
2.12(2)
1.85(2)
2.37
2.9165(19)
2.8844(15)
2.6460(16)
3.295(2)
2
v
C4-H4···O1
vi
C9-H9···N1
0.93
2.55
3.298(3)
138
vii
C6-H6···Cg2
0.93
2.76
3.6862(18)
176
Symmetry codes: [(i) 2− x, 2 − y, 2 – z, (ii) x, 1 + y, z, (iii) 2− x, 1 −
y, 2 – z, (iv) x – 1, y, z, (v) – x, 1–y, 1 – z, (vi) 1 – x, 1 – y, 1 – z (for
1
(
)] and [(i) − x, 1 − y, – z, (ii) 1 – x, 1 – y, – z, (iii) 1 − x, − y, – z,
iv) – x, – y, – z, (v) 1 + x, y, z, (vi) x – 1, y, z – 1, (vii) x, 1 + y, 1 +
z (for 2)]. Cg2 is the centroid of the ring (N2/C9-C13).
3
.2. FT-IR Spectroscopy
-1
The absorption bands observed in the range of 3550–2900 cm are related to the stretching
vibrations of water molecules. The bands for the N–H stretches of amide group of
-1
nicotinamide appear in the range of 3438, 3437 cm . N–H stretching vibrations for Complex
and Complex 2 are observed in the range of 3370-3300 and 3314-3300, respectively. The
1
-1
strong absorption band observed around 1670 cm are assigned to C=O stretching vibration
of carbonyl of amide group of nicotinamide. C=O stretching vibration is observed at 1691 and
1
2

ACCEPTED MANUSCRIPT
-1
1
683 cm for Complex 1 and Complex 2, respectively. Therefore, it is possible to suggest that
carbonyl oxygen of nicotinamide does not participate in the coordination [28].
-1
While nicotinamide pyridine ring vibrations are observed at 1535 cm , those of vibrations of
-1
complexes are shifted to lower frequencies (1447 and 1448 cm ). These shifts indicate that
there is coordination between the nitrogen atom of the nicotinamide ligand and the metal ion.
The asymmetric (υ ) and symmetric (υ ) vibrations of the carboxylate group are observed at
as
s
-1
-1
1
572 and 1369 cm for Complex 1, and at 1574 and 1369 cm for Complex 2. The ꢀυ (υ -
as
-1
υs) values are determined as 203, 204 and 180 cm for Complex 1 and Complex 2,
respectively [16, 38]. The higher ꢀυ values compare to sodium 4-cyanobenzoate salt implies
the monodentate coordination of carboxylate group. The cyano υ(C N) streching vibration of
-1
the 4-cyanobenzoic acid occurs at the almost same frequency ca. 2230 cm it is confirmed
that cyano group is not involved in coordination [16, 39]. FT-IR Spectra of the complexes are
given in S1 and S1.
3
.3. Thermogravimetric Analysis
Thermal decomposition curves of the complexes are given in S3 and S4.
T
he complexes,
Complex 1 and Complex 2, are thermally stable up to 200°C (for 1) and 100°C (for 2),
respectively. The first stage between 225 and 250°C (for Complex 1) and 100 and 300°C (for
Complex 2) corresponds to the endothermic elimination coordinated water molecules with a
mass loss of 5.74% (calcd. 5.66%) (for Complex 1) and 5.71% (calcd. 5.74%) (for Complex
2
). The continuous stages are related to release nicotinamide and 4-cyanobenzoate ligands.
The thermal decomposition products are determined as CuO (for Complex 1) [87.96% (calcd.
8
8.17%)] and NiO (for Complex 2) [87.55% (calcd. 87.45%)], respectively [40, 41].
3
.4. UV-Vis Absorption
The absorption spectrum provides useful information about the energy band structure and the
energy gap values of studied materials. Linear absorption spectra of Complex 1 and 2 thin
1
3

ACCEPTED MANUSCRIPT
films are given in Figure 5. As seen from the figure, Complex 1 and 2 are showing strong
absorption behavior around 450 nm and 350 nm wavelength, respectively. This absorption
*
behavior is consisted of sigma bands. The bands are corresponding to π → π transitions
which involve molecular orbitals essentially are situated in the C N group, benzene and
pyridine rings [42-45]. In addition, Complex 1 and 2 thin films have got absorption peaks
around 715 nm and 646 nm wavelength, respectively. These absorption behaviors are
originating from Q bands. The Q bands of thin film of Complex 1 is redshifted by 69 nm,
when compared to thin film of Complex 2. The observed red spectral shift has been explained
to be due to linear combinations of the atomic orbitals coefficients of the highest occupied
molecular orbital (HOMO) [46, 47]. The energy band gaps (E ) of thin films were estimated
g
with the help of the optical absorption spectra of complex 1 and complex 2 complexes thin
2
films. We plotted (
α
) versus (hν) to determined the band gap values of the films, where
α
is
the absorption coefficient and hν is the photon energy. E values of Complex 1 and Complex
g
2
thin films were found to be 2.412 eV and 3.549 eV, respectively.
Figure 5. Linear absorption spectra of Complex 1 and Complex 2 thin films.
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3
.5. Extinction Coefficient and Refractive Index
The thicknesses of the complex 1 and complex 2 thin films were determined with help of SE
as 201.63 nm and 62.83 nm, respectively. The identifying of the refractive index is very
important for the design of optical materials. The extinction coefficients and linear refraction
indexes related on wavelength of the thin films are given in Figure 6.(a)-(b), respectively. It
can be clearly seen from the Figure 6.(a) that extinction coefficient of complex 1 thin film is
more increasing according to complex 2 thin film with decreasing wavelength. When Figure 5
and Figure 6 are compared, it can be clearly seen that the increasing of the extinction
coefficient of complex 1 thin film with decreasing of the wavelength is consisted of the
increasing of the refractive index rather than alteration of the absorption. As a result, the
complex 1 and complex 2 thin films show different optical behaviors at same wavelengths.
These discrepancies at optical behaviors can be attributed to the difference of film thicknesses
and electronic properties of transition atoms, used.
Figure 6. The extinction coefficients and linear refraction indexes related on wavelength of
the Complex 1 and Complex 2 thin films.
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Conclusion
In the isostructural Complexes 1 and 2, the octahedral metal atom, which rides on a
crystallographic center of symmetry, is coordinated by two monodentate 4-cyanobenzoate
ligands through oxygen atoms of carboxylate groups, two monodentate nicotinamide ligands
through the pyridine ring nitrogen atoms and two water molecules. The band gap values of
thin films of Complex 1 and Complex 2 are estimated from the linear absorption spectra as
2
,412 eV and 3.549 eV, respectively. In addition, from the SE measurements we observed that
the refraction index and extinction coefficients of the thin films increased with decreasing
wavelength. The linear absorption spectra and spectroscopic ellipsometer measurements of
these complexes indicate that they are good candidates for optical filter in the ultraviolet
region.
Acknowledgement
The authors thank the Kafkas University Research Fund for financial support under Grant No.
2
016-FM-49.
Supplementary Data
Crystallographic data for the structural analysis have been deposited with the Cambridge
Crystallographic Data Centre, CCDC 1559802- CCDC 1559803. Copies of this information
may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2
1
EZ, UK.
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Figure Captions
Figure 1. An ORTEP-3 [36] view of 1. The thermal ellipsoids are drawn at the 50%
probability level. Hydrogen bonds are shown as dashed lines.
Figure 2. An ORTEP-3 [36] view of 2. The thermal ellipsoids are drawn at the 50%
probability level.
Figure 3. A partial packing diagram of 1 viewed down [001], where b-axis is horizontal and
a-axis is vertical. Intermolecular N-H···O and O-H···O hydrogen bonds are shown as dashed
lines. Non-bonding H atoms have been omitted for clarity.
Figure 4. A partial packing diagram of 2 viewed down [001], where b-axis is horizontal and
a-axis is vertical . Intermolecular N-H···O and O-H···O hydrogen bonds are shown as dashed
lines. Non-bonding H atoms have been omitted for clarity.
Figure 5. Linear absorption spectra of Complex 1 and Complex 2 thin films.
Figure 6. The extinction coefficients and linear refraction indexes related on wavelength of
the Complex 1 and Complex 2 thin films.
2
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Highlights
•
•
•
•
Cu(II) and Ni(II) 4-cyanobenzoate complexes with nicotinamide were synthesized.
General formula of these complexes is [M(NC-C H COO) (C H N O) (H O) ].
6
4
2
6
6
2
2
2
2
The isostructure complexes have octahedral geometry around the metal atom center.
These complexes are good candidates for optical filter in the ultraviolet region.