Hydrothermal preparation, crystal structure, a series of properties and theoretical calculation of a novel cadmium compound

Article abstract of DOI:10.1080/24701556.2020.1735430

A novel cadmium compound [CdL(bipy)₂]·6H₂O was synthesized by hydrothermal method, and its crystal structure was determined by single-crystal X-ray diffraction. The title compound crystallized in the monoclinic system of the C2/c space group, and existed as an isolated monocyte structure. The strong π…π stacking interactions produces one-dimensional (1-D) chains and a three-dimensional (3-D) supramolecular structure is formed by a large number of intermolecular hydrogen bonds. A series of properties of the title compound were tested by solid state photoluminescence, CIE analysis and solid-state diffuse reflectance, and the charge transfer of the title compound was studied by time-dependent density functional theory.

Full text of DOI:10.1080/24701556.2020.1735430

Inorganic and Nano-Metal Chemistry
ISSN: 2470-1556 (Print) 2470-1564 (Online) Journal homepage: https://www.tandfonline.com/loi/lsrt21
Hydrothermal preparation, crystal structure, a
series of properties and theoretical calculation of
a novel cadmium compound
Yin-Feng Wang, Xiu-Guang Yi, Xiao-Niu Fang, Jia Li, Yao Xu & Shi-Kun Xie
To cite this article: Yin-Feng Wang, Xiu-Guang Yi, Xiao-Niu Fang, Jia Li, Yao Xu & Shi-Kun
Xie (2020): Hydrothermal preparation, crystal structure, a series of properties and theoretical
calculation of a novel cadmium compound, Inorganic and Nano-Metal Chemistry, DOI:
10.1080/24701556.2020.1735430
To link to this article: https://doi.org/10.1080/24701556.2020.1735430
View supplementary material
Published online: 10 Mar 2020.
Submit your article to this journal
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
https://www.tandfonline.com/action/journalInformation?journalCode=lsrt21

INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2020.1735430
Hydrothermal preparation, crystal structure, a series of properties and
theoretical calculation of a novel cadmium compound
Yin-Feng Wanga, Xiu-Guang Yia, Xiao-Niu Fanga, Jia Lia, Yao Xua, and Shi-Kun Xieb
b
aSchool of Chemistry and Chemical Engineering, Jinggangshan University, Ji’an, Jiangxi, China; School of Mechanical and Electrical
Engineering, Jinggangshan University, Ji’an, Jiangxi, China
ABSTRACT
ARTICLE HISTORY
Received 29 December 2019
Accepted 15 February 2020
A novel cadmium compound [CdL(bipy)2]ꢀ6H2O was synthesized by hydrothermal method, and its
crystal structure was determined by single-crystal X-ray diffraction. The title compound crystallized
in the monoclinic system of the C2/c space group, and existed as an isolated monocyte structure.
The strong p … p stacking interactions produces one-dimensional (1-D) chains and a three-dimen-
sional (3-D) supramolecular structure is formed by a large number of intermolecular hydrogen
bonds . A series of properties of the title compound were tested by solid state photolumines-
cence, CIE analysis and solid-state diffuse reflectance, and the charge transfer of the title com-
pound was studied by time-dependent density functional theory.
KEYWORDS
Cadmium; crystal structure;
semiconductor;
photoluminescence; TDDFT
Introduction
as the calculation of time-dependent density functional the-
ory (TDDFT).
Recently, in the field of chemistry and materials, inorganic-
organic hybrid materials have been paid more and more
attention by chemists and material scientists, owing to their Experimental
potential applications in optical materials,[1] semiconductor
Materials and physical measurements
materials,[2] magnetic materials[3] and medical materials[4]
and so on.
The reagents and chemicals used to synthesize the title com-
pound are analytical reagent grade, which can be sold on
Quinoline carboxylic acids are a kind of versatile sub-
stance. Many quinoline carboxylic acids possess biological the market and can be used without further purification.
activity, such as antibacterial activities,[5,6] anti-inflammatory The infrared spectra is obtained from the PE Spectrum-One
and analgesic activity,[7] antileihmanial activity,[8] inhibitors Fourier transform infrared (FT-IR), the 1H NMR spectra
of dihydroorotate dehydrogenase,[9] anticancer activity,[10] were measured on Bruker Avance 400 MHz instrument
and so on. Recently, due to the synergistic effect from using DMSO as solvent, the photoluminescence was meas-
ured on the F97XP photoluminescence spectrometer, the
solid-State UV/Vis reflectance spectroscopy was determined
with a TU1901 UV/Vis spectrometer equipped with an inte-
grating sphere. TDDFT investigations were performed using
the Gaussian 09 suite of program packages.
coordination modes of quinoline carboxylic acid ligand and
anion effect, many quinoline carboxylic acids can be used as
the main ligand to construct the supramolecular metal com-
plexes with luminescent activity and biological activity, such
as lanthanide complexes,[11] Dy(III) complexes,[12] Cd(II)
complexes,[13,14] etc.
Because of the special interest in quinoline carboxylic
acids, a series of transition metal complexes with 3-hydroxy-
2-methylquinoline-4-carboxylic acid as the main ligand were
Synthesis of HL (HL 5 3-hydroxy-2-methylquinoline-4-
carboxylic acid)
synthesized and reported by Yi’s group, such as, mono- The Synthesis of HL ligands mainly refers to the relevant
synthesis literatures, as shown in Scheme 1.[20]
nuclear Zn(II)/Ni(II)/Pr(III) complexes with monodentate
coordination,[15–17] mononuclear Cu(II)/Zn(II) complexes
with bidentate chelated coordination.[18–20]
Synthesis of the title compound [CdL(bipy)2]ꢀ6H2O
In the continuing of our work, we report here the hydro-
thermal synthesis, X-ray crystal structure, photoluminescent, The
mixture
containing
HL
(203 mg,
1 mmol),
and semiconductor properties of the title compound, as well Cd(CH3COO)2ꢀ2H2O (170 mg, 1 mmol), bipy (312 mg,
CONTACT Xiu-Guang Yi
jayxgggchem@163.com
School of Chemistry and Chemical Engineering, Jinggangshan University, Ji’an, Jiangxi 343009, China, Shi-
Kun Xie xskun@163.com School of Mechanical and Electrical Engineering, Jinggangshan University, Ji’an, Jiangxi 343009, China.
Supplemental data for this article can be accessed at the publisher’s website.
ß 2020 Taylor & Francis Group, LLC

2
Y.-F. WANG ET AL.
Scheme 1. Synthetic route of ligand HL.
Table 1. Summary of crystal data.
Table 2. Selected bond lengths (Å) and bond angle (ꢁ).
Distance
(Å)
Distance
(Å)
Empirical formula
C31H36CdN5O9
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
735.05
293(2)
monoclinic
C2/c
24.9724(9)
17.7565(7)
15.3771(5)
90
105.862(3)
90
6558.9(4)
8
1.489
0.726
3016.0
Cd(1)–O(1)
Cd(1)–O(2)
Cd(1)–N(3)
Angle
O(1)–Cd(1)–N(1)
O(1)–Cd(1)–O(2)
O(1)–Cd(1)–N(2)
O(1)–Cd(1)–N(3)
O(1)–Cd(1)–N(4)
O(2)–Cd(1)–N(1)
O(2)–Cd(1)–N(2)
O(2)–Cd(1)–N(3)
2.2330(19)
2.285(2)
2.364(2)
(ꢁ)
95.71(7)
83.64(8)
109.98(8)
153.99(8)
91.65(8)
154.28(9)
86.21(9)
86.93(9)
Cd(1)–N(1)
Cd(1)–N(2)
Cd(1)–N(4)
Angle
O(2)–Cd(1)–N(4)
N(2)–Cd(1)–N(1)
N(2)–Cd(1)–N(3)
N(2)–Cd(1)–N(4)
N(3)–Cd(1)–N(1)
N(3)–Cd(1)–N(4)
N(4)–Cd(1)–N(1)
2.385(2)
2.356(2)
2.366(2)
(ꢁ)
112.04(9)
69.56(9)
93.48(8)
153.51(10)
103.08(9)
69.56(9)
93.68(9)
c/Å
a/ꢁ
b/ꢁ
c/ꢁ
Volume/Å3
Z
qcalcg/cm3
l/mm-1
(0.0506P)2 þ 9.855P]), where P ¼ (Fo þ 2Fc )/3);
S ¼ 1.041, (Dq)max ¼ 1.09 and (Dq)min ¼ ꢂ0.42 e/Å3.
Tables 1 and 2 provide a summary of the crystallographic
data, selected bond lengths and of the title compound,
respectively.
2
2
F(000)
Crystal size/mm3
Radiation
0.38 ꢃ 0.27 ꢃ 0.21
MoKa (k ¼ 0.71073)
6.604 to 52.744
ꢂ31 ꢄ h ꢄ 31, ꢂ22 ꢄ k ꢄ 22,
ꢂ19 ꢄ l ꢄ 19
2H range for data collection/ꢁ
Index ranges
Reflections collected
35454
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indexes [I ꢅ 2r (I)]
Final R indexes [all data]
Largest diff. peak/hole/e Åꢂ3
6698 [Rint¼ 0.0251, Rsigma¼ 0.0190]
6698/0/443
1.041
Results and discussion
R1¼ 0.0367, wR2¼ 0.0945
R1¼ 0.0462, wR2¼ 0.1021
1.09/ꢂ0.42
The preparation of the title compound is as follows: first,
indigo is oxidized by K2CrO7 to form the intermediate
product isatin. Second, the ligand HL was obtained by add-
ing chloroacetone to the intermediate isatin in alkaline con-
dition. Finally, the title compound was synthesized by
hydrothermal reaction of the HL with cadmium acetate,
2,20-bipyridine, water and triethylamine. According to the
infrared spectrum of the title compound [CdL(bipy)2]ꢀ6H2O,
the strong broad band at 3437 cmꢂ1 indicates the presence
of water, the absorption at 1631 cmꢂ1 is assigned to the con-
tribution of C¼N, the absorptions at 1595 cmꢂ1 and
1355 cmꢂ1 are considered as the presence of monodentated
carboyxlate in the title compound, as shown in Figure 1.
This compound crystallizes in the monoclinic C2/c. The
asymmetric unit contains of one cadmium (II) ion, one
quinoline carboxylic acid anion, two bipy molecules and six
lattice water molecules, as shown in Figure 2. The cadmium
R1 ¼ RjjFojꢂjFcjj/RjFoj; wR2 ¼ fR[w(Fo ꢂFc ]/ R[wFo2]2g1/2.
2
2
2 mmol), H2O (9 mL), and triethylamine (1 mL) was placed
in a 25 mL polytetrafluoroethylene lined autoclave and
heated to 100 ꢁC for 7 days under autogenous pressure.
When the reaction mixture was cooled down room tempera-
ture, bright yellow block-like crystals were obtained, which
is used to collect single crystal X-ray data and infrared spec-
troscopy. The yield was 75% base on [CdL(bipy)2]ꢀ6H2O. IR
peaks (cmꢂ1): 3437(vs), 1631(w), 1595(m), 1562(w), 1434(s),
1355(w), 1310(w), 768(m).
Crystallographic data collection and refinement
The single crystal data of the title compound were collected
with a suitable single crystal (size 0.38 mm ꢃ 0.27 mm ꢃ atom has hexacoordinated by two oxygen atoms (O(1) and
0.21 mm) on a SuperNova charge-coupled device (CCD) X- O(2)) from quinoline carboxylic acid and four nitrogen
ray diffractometer. During the data acquisition, the crystal atoms (N(1), N(2), N(3) and N(4)) from two bipys in a dis-
temperature was kept at 292(2) K. Using Olex2,[21] the struc- torted octahedron geometry. The Cd (II) ion occupies the
ture was solved with the olex2.solve[22] structure solution center of octahedron, N(1) and O(2) occupy axial position,
program using Charge Flipping and refined with the ShelXL and N(2), N(3), N(4), O(1) occupy the equatorial plane of
refinement package[23] (using Least Squares minimisation). octahedron, respectively. The bond distances of Cd–O(1)
All of the non hydrogen atoms were generated based on the and Cd–O(2) are 2.2330(19) Å and 2.285(2) Å, respectively,
subsequent Fourier difference diagram and were refined ani- while those of Cd–N(1), Cd(1)–N(2), Cd(1)–N(3) and
sotropically. The hydrogen atoms were located theoretically Cd–N(4) are 2.385(2) Å, 2.356(2) Å, 2.364(2) Å and
and ride on their parent atoms. The final refining results 2.366(2) Å. These are comparable with that reported in the
were given R ¼ 0.0367, wR ¼ 0.0945(w ¼ 1/[r2(Fo )
þ
references.[24,25] Both the quinolinecarboxylate (L–) and bipy
2

INORGANIC AND NANO-METAL CHEMISTRY
3
act as the bidentate ligand, which occupy the basal position. 1/2 þ z)), thus forming a three-dimensional supramolecular
The title compound also contains six lattice water molecules. structure, as shown in Figure 3 and Table 3, respectively.
There are not only a A lot of intramolecular hydrogen
bonds, which can be found the O–H bond and O
atom(O(5)–H(5A)ꢀꢀꢀO(8); O(8)–H(8A)ꢀꢀꢀO(2); O(8)–H(8B)
ꢀꢀꢀO(7)), but also a lot of intermolecular hydrogen bonds,
In the title compound, there are also strong offset face-
to-face p … p stacking interaction between Cg3ꢀꢀꢀCg6i,
Cg4ꢀꢀꢀCg5ii [Cg3 is N2/C5/C6/C7/C8/C9, Cg4 is N4/C20/
C21/C22/C23/C24, Cg5 is N3/C15/C16/C17/C18/C19, Cg6 is
N1/C10/C11/C12/C13/C14; i ¼ 1 ꢂ x, 1 ꢂ y, 1 ꢂ z; ii ¼ 3/
2 ꢂ x, 1/2x ꢂ y, 1 ꢂ z]. The centroid–centroid distance of
Cg1 … Cg6i is 3.629 Å with the shift distance being of
0.275 Å and the twist angle being of 10.528ꢁ. The centroid-
centroid distance of Cg4ꢀꢀꢀCg5ii is 3.919 Å with the shift dis-
tance being of 1.719 Å and the twist angle being of 177.906ꢁ.
These pꢀꢀꢀp stacking interactions and via van de Waals
attraction yield the one-dimensional supramolecular struc-
ture, the crystal packing as presented in Figure 4. There are
also two interactions between C–HꢀꢀꢀCg (pꢀꢀꢀRing) in
the one-dimensional structure, they are C13–H13ꢀꢀꢀCg8 (N5/
C25/C26/C28/C30/C35; x,1 ꢂ y,1/2 þ z) and C18–H18ꢀꢀꢀCg8
which can be found the O–H bond and
O atom
(O(4)–H(4A)ꢀꢀꢀO(5), (Symmetric code: 3/2 ꢂ x, 1/2 þ y, 3/
2 ꢂ z);
O(4)–H(4B)ꢀꢀꢀO(9),
(1/2 þ x,
1/2 þ y,
z);
O(6)–H(6A)ꢀꢀꢀO(5), (3/2 ꢂ x,1/2 ꢂ y,1 ꢂ z); O(7)–H(7A)
ꢀꢀꢀO(4), (3/2 ꢂ x,1/2 ꢂ y,1 ꢂ z); O(7)–H(7B)ꢀꢀꢀO(5) (1 ꢂ x,
ꢂy,1 ꢂ z), the N–H bond and O atom (N(5)–H(5)ꢀꢀꢀO(6),
(Symmetric code: x, 1 ꢂ y, ꢂ1/2 þ z)) and the O–H bond
and N atom(O(6)–H(6B)ꢀꢀꢀN(5), (Symmetric code: x, 1 ꢂ y,
(N5/C25/C26/C28/C30/C35;
respectively.
3/2 ꢂ x,1/2 ꢂ y,1 ꢂ z),
Based on barium sulfate as the reference for 100% reflect-
ivity, the UV–Vis diffuse reflectance spectra of the target
compound was measured at room temperature, using the
solid-state compound. Data processing adopts (ahꢀ)1/n
¼
A(hꢀꢂEg), which is the famous Tauc plot formula,[26,27]
where a is the absorption coefficient, h is the Planck’s con-
stant (6.63 ꢃ 10ꢂ34J.s), ꢀ is the frequency, A is the constant
and Eg is the band gap of semiconductor. First, the (ahꢀ)1/n
(n ¼ 1/2) and hꢀ are obtained by using the solid-state
UV–Vis diffuse reflectance spectrum, where hꢀ ¼ hc/k, k is
the wavelength of light. Second, the graph is draw with
(ahꢀ)1/n as the vertical coordinate and hꢀ (1 eV
¼
Figure 1. FTIR spectra of the title complex [CdL(bipy)2]ꢀ6H2O.
Figure 2. The monomolecular diagram of the title complex. The hydrogen atoms of the lattice water molecules are omitted for clarity.

4
Y.-F. WANG ET AL.
Figure 3. The packing diagram of the title complex with the dashed lines representing the hydrogen interactions.
Table 3. Hydrogen bond lengths (Å) and bond angles (ꢁ).
1.6 ꢃ 10ꢂ19 J) as the horizontal coordinate. Finally, the
straight part of the figure is extrapolated to the horizontal
coordinate, and the intersection point is the energy band
gap. As shown in Figure 5, the title compound shows a
broad optical energy band gap of 2.61 eV. Therefore, this
may be a candidate material for broad band gap semicon-
ductors. The energy band gap of 2.61 eV of the title com-
pound is obviously larger than those of GaAs (1.4 eV), CdTe
(1.5 eV), and CuInS2 (1.55 eV),[28–30] those are called effi-
cient band gap photovoltaic materials.
D–H … A
[ARU]
D–H (Å) H … A(Å) D … A(Å) D–H … A (ꢁ)
O(4)–H(4A)ꢀꢀꢀO(5) [6656] 0.85
O(4)–H(4B)ꢀꢀꢀO(9) [5555] 0.85
2.29
2.36
2.05
1.93
2.05
2.19
2.24
2.14
2.32
2.27
2.763(14)
2.958(16)
2.882(6)
2.722(11)
2.758(10)
2.882(6)
2.846(11)
2.776(11)
2.960(8)
115
128
162
154
132
139
128
131
133
107
N(5)–H(5)ꢀꢀꢀO(6)
O(5)–H(5A)ꢀꢀꢀO(8)
[4565] 0.86
0.85
O(6)–H(6A)ꢀꢀꢀO(5) [7656] 0.94
O(6)–H(6B)ꢀꢀꢀN(5) [4564] 0.85
O(7)–H(7A)ꢀꢀꢀO(4) [7656] 0.85
O(7)–H(7B)ꢀꢀꢀO(5) [3656] 0.85
O(8)–H(8A)ꢀꢀꢀO(2)
0.85
0.85
O(8)–H(8B)ꢀꢀꢀO(7)
2.649(14)
Symmetric code: [4565] ¼ x, 1 ꢂ y, 1/2 þ z; [4564] ¼ x, 1 ꢂ y, ꢂ1/2 þ z ;
[5555] ¼ 1/2 þ x, 1/2 þ y, z ; [6656] ¼ 3/2 ꢂ x, 1/2 þ y, 3/2 ꢂ z; [7656] ¼ 3/
2 ꢂ x, 1/2 ꢂ y, 1 ꢂ z; [3656] ¼ 1 ꢂ x, ꢂy, 1 ꢂ z.
At the same time, in order to reveal the potential photo-
luminescence characteristics of the title compound, the
Figure 4. The p … p stacking interactions diagram of the title complex. The lattice water molecules are omitted for clarity.

INORGANIC AND NANO-METAL CHEMISTRY
5
photoluminescence spectra of the solid state samples at the title compound located in the blue region with the
CIE1931 chromaticity coordinate (0.1568, 0.0183) (Figure 7).
Therefore, the title compound is a potential blue light-emit-
ting material.
room temperature were measured, and the results are shown
in Figure 6. It can be seen that the photoluminescence spec-
trum of the title compound shows an effective energy
absorption in the wavelength range of 250–470 nm. Upon
445 nm emission, the excitation spectrum shows a band at
522 nm. Under the excitation of 522 nm, there is a sharp
band in the blue region of 445 nm. The emission band of
In addition, in order to reveal the nature of the photolu-
minescence properties of the title compound, we truncated
ground state geometry from its single crystal X-ray diffrac-
tion data set without optimization, and on this basis, we cal-
culated it according to the time-dependent density
functional theory (TDDFT). TDDFT calculations were calcu-
lated with the nine functions, including B3LYP, B3PW91,
mPW3PBE, PBEh1PBE, HSEH1PBE, PBEPBE, M06-L, M06-
2X, and BLYP, the base set of SDD for Cd and the base set
ꢆ
of 6-31 G for C, H, O, N, and it were done with the
Gaussian09 program.[31] The characteristics of HOMO and
LUMO of the title compound are shown in Figure 8. From
Table 4, it can be found that the egap value obtained at TD-
B3LYP, TD-B3PW91, and TD-mPW3PBE methods are
almost the same. Then, the results at TD-B3LYP method
were used in the following discussion. From the figure, we
Figure 5. The solid-state UV–Vis diffuse reflectance spectrum (Eg ¼ 2.61 eV).
The inset is the UV–Vis spectra of the title complex.
Figure 6. Photoluminescence properties of the title complex (red: emission
curve; blue: excitation curve).
Figure 7. The CIE diagram of the emission spectrum of the title complex.
Figure 8. HOMO and LUMO of the title complex with isosurface of 0.03 a.u.

6
Y.-F. WANG ET AL.
Table 4. Energy of HOMO (eHOMO, eV), LUMO (eLUMO, eV), and HOMO-LUMO
gap (egap, eV) with different methods.
7. Boyarshinov, V.-D.; Mikhalev, A.-I.; Yushkova, T.-A.; Ukhov, S.-
V.; Kon’shina, T.-M. Synthesis and Biological Activity of
Quinoline-2-Carboxylic Acid Aryl Esters and Amides. Pharm.
Chem. J. 2017, 51, 351–354. DOI: 10.1007/s11094-017-1613-4.
8. Abdelwahid, M.-A.-S.; Elsaman, T.; Mohamed, M.-S.; Latif, S.-A.;
Mukhtar, M.-M.; Mohamed, M.-A. Synthesis, Characterization,
and Antileishmanial Activity of Certain Quinoline-4-carboxylic
Acids. J. Chem. 2019, 2019, 9. DOI: 10.1155/2019/2859637.
9. Madak, J. T.; Cuthbertson, C. R.; Miyata, Y.; Tamura, S.;
Petrunak, E. M.; Stuckey, J. A.; Han, Y.; He, M.; Sun, D.;
Showalter, H. D.; Neamati, N. Design, Synthesis, and Biological
Evaluation of 4-Quinoline Carboxylic Acids as Inhibitors of
Dihydroorotate Dehydrogenase. J. Med. Chem. 2018, 61,
5162–5186. DOI: 10.1021/acs.jmedchem.7b01862.
eHOMO
eLUMO
egap
TD-B3LYP
ꢂ3.448
ꢂ3.543
ꢂ3.554
ꢂ3.695
ꢂ3.328
ꢂ3.059
ꢂ3.056
ꢂ4.746
ꢂ2.814
ꢂ2.427
ꢂ2.536
ꢂ2.544
ꢂ2.354
ꢂ2.713
ꢂ2.898
ꢂ2.890
ꢂ1.595
ꢂ2.675
1.020
1.007
1.010
1.342
0.615
0.161
0.166
3.151
0.139
TD-B3PW91
TD-mPW3PBE
TD-PBEh1PBE
TD-HSEH1PBE
TD-PBEPBE
TD-M06-L
TD-M06-2X
TD-BLYP
can find that the electron density distribution of HOMO
was completely located in the p-orbital of HL with an
energy of ꢂ3.448 eV (eHOMO); while that of LUMO was
completely located in the p-orbital of bipy, with an energy
of eLUMO ¼ ꢂ2.427 eV. The energy difference (egap ¼
1.020 eV) between LUMO and HOMO is small enough to
transfer the charge from HOMO to LUMO. According to
this observation, we can get that the nature of photolumi-
nescence of the title compound is attributed to the ligand-
to-ligand charge transfer (LLCT; from the p-orbital HOMO
of ligand HL to the p-orbital LUMO of ligand bipy).
10. Bhatt, H. G.; Agrawal, Y. K.; Patel, M. J. Amino- and Fluoro-
Substituted Quinoline-4-Carboxylic Acid Derivatives: MWI
Synthesis, Cytotoxic Activity, Apoptotic DNA Fragmentation
and Molecular Docking Studies. Med. Chem. Res. 2015, 24,
1662–1671. DOI: 10.1007/s00044-014-1248-x.
11. Zhang, H.-J.; Fan, R.-Q.; Wang, P.; Wang, X.-M.; Gao, S.; Dong,
Y.-W.; Wang, Y.-L.; Wang, Y.-L. Structure Variations of a Series
of Lanthanide Complexes Constructed from Quinoline
Carboxylate Ligands: photoluminescent Properties and PMMA
Matrix Doping. Rsc Adv. 2015, 5, 38254–38263. DOI: 10.1039/
C5RA01796C.
12. Bai, J.; Zhang, C.; Tang, J.-X.; Wang, H.-L.; Zou, H.-H. Crystal
Structure, Magnetic Properties and Multiplex Photoluminescence
of Dy-Exclusive Coordination Polymer Based on Quinoline-2-
Carboxylic Acid. Inorg. Chim. Acta 2019, 492, 182–185. DOI: 10.
1016/j.ica.2019.04.027.
Funding
13. Zhang, L.; Man, Z.-W.; Zhang, Y.; Hong, J.; Guo, M.-R.; Qin, J.
Synthesis, Structure Evaluation, Spectroscopic and Antibacterial
Investigation of Metal Complexes with 2-(Pyridin-4-
yl)Quinoline-4-Carboxylic Acid. Acta Chim Slov. 2016, 63,
891–989. DOI: 10.17344/acsi.2016.2895.
The work was supported by the National Natural Science of
Foundation of China (No.51363009, 1965015), Natural Science
Foundation of Jiangxi Province of China(20181BAB206028), Jiangxi
Province Department of Education’s Item of Science and Technology
& Higher Education and Teaching Reform (GJJ190550, GJJ160732,
JXJG-17-9-14), Doctoral Research Startup Foundation and Natural
Science Foundation Project of Jinggangshan University (JZB1905).
14. Pan, G.-H.; Tang, J.-N.; Yin, X.-H.; Xu, W.-J.; Huang, Z.-J.
Synthesis,
Structures,
Electrochemical
Analysis,
and
Luminescence Properties of Four Supramolecular Complexes
Based on Quinoline-2-Carboxylic Acid. Synth. React. Inorg. M.
2014, 44, 848–858. DOI: 10.1080/15533174.2013.791848.
15. Yi, Z.-Q.; Fang, X.-N.; Cao, Z.-Y.; Wei, Y.; Li, Y.-J.; Yi, X.-G.
Preparation, Photoluminescence, Semiconductor Properties, and
Theoretical Calculations for a Novel Zinc Zero-Dimensional
Structure Complex. J. Chem. Res. 2019, 43, 58–62. DOI: 10.1177/
1747519819831886.
16. Fang, X.-N.; Li, J.; Yi, X.-G.; Luo, Q.; Chen, J.-Y.; Li, Y.-X.
Preparation, Structure, Photoluminescent and Semiconductive
Properties, and Theoretical Calculation of a Mononuclear Nickel
References
1. Chen, H.; Lyu, G.; Yue, Y.; Wang, T.; Li, D.-P.; Shi, H.; Xing, J.;
Shao, J.; Zhang, R.; Liu, J. Improving the Photovoltaic
Performance by Employing Alkyl Chains Perpendicular to the
p-Conjugated Plane of an Organic Dye in Dye-Sensitized Solar
Cells. J. Mater. Chem. C 2019, 7, 7249–7258. DOI: 10.1039/
C9TC01520E.
2. Ji, Q.; Li, L.; Deng, S.; Chen, L. High Switchable Dielectric Phase
Transition Originating from Distortion in Inorganic–Organic
Hybrid Materials (H2dabco-C2H5) [MIICl4] (M ¼ Co, Zn).
Dalton Trans. 2018, 47, 5630. DOI: 10.1039/c8dt00623g.
3. Patel, K.; Zhang, J.; Ren, S. Rare-Earth-Free High Energy
Product Manganese-Based Magnetic Materials. Nanoscale 2018,
10, 11701–11718. DOI: 10.1039/C8NR01847B.
Complex
with
3-Hydroxy-2-Methylquinoline-4-Carboxylato
Ligand. Acta Chim. Slov. 2019, 66, 414–420. DOI: 10.17344/acsi.
2018.4885.
17. Yi, X.-G.; Liu, Y.-Z.; Fang, X.-N.; Zhou, X.-Y.; Li, Y.-X. Crystal
Structure and Properties of [PrCl(H2O)3(L)(HL)]n nCl (HL ¼ 3-
Hydroxy-2-methylquinoline-4-carboxylicacid) with One-dimen-
sional Chains. Chinese J. Struct. Chem. 2019, 38, 325–330. DOI:
10.14102/j.cnki.0254-5861.2011-2065
ꢀ
4. Wu, T.; Bour, P.; Andrushchenko, V. Europium (III) as a
18. Fang, X.-N.; Li, J.; Yi, X.-G.; Yi, Z.-Q.; Chen, J.-Y.; Li, Y.-X.
Synthesis, Crystal Structure, Theoretical Calculation and
Circularly Polarized Luminescence Probe of DNA Structure. Sci.
Rep. 2019, 9, 1068. DOI: 10.1038/s41598-018-37680-7.
5. Wang, X.; Xie, X.; Cai, Y.; Yang, X.; Li, J.; Li, Y.; Chen, W.; He,
M. Design, Synthesis and Antibacterial Evaluation of Some New
2-Phenyl-Quinoline-4-Carboxylic Acid Derivatives. Molecules
2016, 21, 340. DOI: 10.3390/molecules21030340.
6. Suresh, N.; Nagesh, H.-N.; Renuka, J.; Rajput, V.; Sharma, R.;
Khan, I.-A.; Gowri, C. Synthesis and Evaluation of 1-cyclo-
propyl-6-fluoro-1,4-dihydro-4-oxo-7-(4-(2-(4-substitutedpipera-
Properties
of
Cu(II)
Complex
with
3-Hydroxy-2-
Methylquinoline-4-Carboxylic acid. Chinese J. Inorg. Chem. 2019,
35(5), 930–936.
19. Li, J.; Shi, L.-S.; Yi, X.-G.; Fang, X.-N.; Guo, T.; Li, Y.-X.
Synthesis, Crystal Structure and Catalytic Properties of a 2D
Cobalt(II) Coordination Polymer Based on Mixed Ligands.
Chinese J. Struct. Chem. 2020,39(3),1–10. DOI:10.14102/j.cnki.
0254-5861.2011-2475..
zin-1-yl)acetyl)piperazin-1-yl)quinoline-3-carboxylic
acid
20. Yi, X.-G.; Fang, X.-N.; Guo, J.; Li, J.; Xie, Z.-P. Hydrothermal
Preparation, Crystal Structure, Photoluminescence and UV-
Visible Diffuse Reflectance Spectroscopic Properties of a Novel
Derivatives as Anti-tubercular and Antibacterial Agents. Eur. J.
Med. Chem. 2014, 71, 324–332. DOI: 10.1016/j.ejmech.2013.10.
055.

INORGANIC AND NANO-METAL CHEMISTRY
7
Mononuclear Zinc Complex. Acta Chim. Slov. 2020, 67. DOI: 26. Tuac, J.; Grigorovici, R.; Vancu, A. Optical Properties and
Electronic Structure of Amorphous Germanium. Phys. Stat. Sol.
(b) 1966, 15, 627. DOI: 10.1002/pssb.19660150224.
27. Davis, E.-A.; Mott, N.-F. Conduction in Non-Crystalline Systems
V. Conductivity, Optical Absorption and Photoconductivity in
Amorphous Semiconductors. Philos. Mag. 1970, 22, 903–822.
DOI:10.1080/14786437008221061.
28. Lin, W.-S.; Chen, W.-T. Photoluminescence and Semiconductive
Properties of a 4f–5d Compound. J. Iran. Chem. Soc. 2019, 16,
2473–2478. DOI: 10.1007/s13738-019-01715-1.
29. Du}richen, P.; Bensch, W. K6Nb4S25, the First Ternary Niobium
Polysulfide Exhibiting the Complex Anion (Nb4S25)6-:
Preparation and Crystal Structure Determination. Eur. J. Solid
State Inorg. Chem. 1997, 34, 1187–1198.
30. Tillinski, R.; Rumpf, C.; N€ather, C.; Du€richen, P.; Jeß, I.; Schunk,
S. A.; Bensch, W. Synthesis, Crystal Structures, and Optical Properties
of New Quaternary Metal Chalcogenides of Group 5: Cs2AgVS4,
K2AgVSe4, Rb2AgVSe4, Rb2AgNbS4, and Cs2AgNbSe4. Z Anorg.
Allg. Chem. 1998, 624, 1285–1290. DOI: 10.1002/(SICI)1521-
3749(199808)624:8<1285::AID-ZAAC1285>3.0.CO;2-5.
10.1734/4.acsi.2019.5532.
21. Dolomanov, O.-V.; Bourhis, L.-J.; Gildea, R.-J.; Howard, J.-A.-K.;
Puschmann, H.-J. OLEX2 : A Complete Structure Solution,
Refinement and Analysis Program. J. Appl. Crystallogr. 2009, 42,
339–341. DOI: 10.1107/S0021889808042726.
22. Bourhis, L.-J.; Dolomanov, O.-V.; Gildea, R.-J.; Howard, J.-A.-K.;
Puschmann, H.-J. The Anatomy of
a
Comprehensive
Constrained, Restrained Refinement Program for the Modern
Computing Environment – Olex2 Dissected. Acta Crystallogr. A
Found. Adv. 2015, 71, 59–75. DOI: 10.1107/S2053273314022207.
23. Sheldrick, G.-M. Crystal Structure Refinement with SHELXL.
Acta Crystallogr. C Struct. Chem. 2015, 71, 3–8. DOI: 10.1107/
S2053229614024218.
24. Nallasami, P.; Palanisarmy, R.; Ramaswmy, M. Non-Covalently
Aggregated Zinc and Cadmium Complexes Derived from
Substituted Aromatic Carboxylic Acids: Synthesis, Spectroscopy,
and Structural Studies. Inorg. Chim. Acta 2013, 405, 522–531.
DOI:10.1016/j.ica.2013.04.021.
25. Zhang, X.-J.; Tian, Y.-P.; Li, S.-L.; Jiang, M-h.; Usman, A.;
Chantrapromma, S.; Fun, H.-K. Zn(II) and Cd(II) N-
Carbazolylacetates with Strong Fluorescence. Polyhedron 2003,
22, 397–402. DOI: 10.1016/S0277-5387(02)01360-8.
31. Frisch, M.-J.; Trucks, G.-W.; Schlegel, H.-B.; Scuseria, G.-E.;
Robb, M.-A.; Cheeseman, J.-R.; Scalmani Barone, G. V.;
Mennucci, B.; Petersson, G.-A.; et al. Fox, Gaussion 09(Revision
D.01); Gaussian, Inc.: Wallingford, CT, 2013.