Syntheses, crystal structures, UV-Vis absorption, and fluorescent properties of a complex: [btx][Cu2I4]

Article abstract of DOI:10.1080/15533174.2011.611205

The self-assembly reaction of organic cation and metal iodides yielded a novel binuclear coordination compound, namely [btx][Cu₂I4](1) [btx = 1,6-bis(triethylmethylammonium)xylol], which is characterized by X-ray crystallography, IR spectroscopy, fluorescence spectra, and UV-vis absorption spectra. The compound 1 crystallizes in Monoclinic, space group P2(1)/c with a = 8.2246(12), b = 11.5843(17), c = 15.005(2), α= 90, = 94.218(2)°, γ= 90°. In the anion [Cu₂I₄]^2-, each Cu center is triangularly coordinated by two μ₂-I(2) atoms and one terminal I(1) atom. The organic cationic [btx]²⁺ existed around it through supramolecular interactions. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.611205

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Syntheses, Crystal Structures, UV-Vis Absorption, and
Fluorescent Properties of a Complex: [btx][Cu2I4]
Hai-Juan Du a , Yu Liang b , Ling-Fang Wang a & Yun-Yin Niu a
a Department of Chemistry , Zhengzhou University , Zhengzhou , P. R. China
b College of Chemistry and Chemical Engineering , Xinxiang University , Xinxiang , P. R.
China
Accepted author version posted online: 14 Mar 2012.Published online: 24 Apr 2012.
To cite this article: Hai-Juan Du , Yu Liang , Ling-Fang Wang & Yun-Yin Niu (2012) Syntheses, Crystal Structures, UV-Vis
Absorption, and Fluorescent Properties of a Complex: [btx][Cu2I4], Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry, 42:3, 364-368, DOI: 10.1080/15533174.2011.611205
To link to this article: http://dx.doi.org/10.1080/15533174.2011.611205
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:364–368, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.611205
Syntheses, Crystal Structures, UV-Vis Absorption,
and Fluorescent Properties of a Complex: [btx][Cu2I4]
Hai-Juan Du,1 Yu Liang,2 Ling-Fang Wang,1 and Yun-Yin Niu1
1Department of Chemistry, Zhengzhou University,, Zhengzhou, P. R. China
2College of Chemistry and Chemical Engineering, Xinxiang University, Xinxiang, P. R. China
a novel binuclear coordination compound [btx][Cu2I4](1) [btx
= 1,6-bis(triethylmethylammonium)xylol]. It is characterized
by single-crystal X-ray diffraction, IR spectroscopy, fluores-
cence spectra, and UV-vis absorption spectra. Moreover, in an-
ion [Cu2I4]2−, each Cu center is triangularly coordinated by two
µ2-I(2) atoms and one terminal I(1) atom. The organic cationic
[btx]2+ existed around it through supramolecular interactions.
The self-assembly reaction of organic cation and metal io-
dides yielded a novel binuclear coordination compound, namely
[btx][Cu2I4](1) [btx = 1,6-bis(triethylmethylammonium)xylol],
which is characterized by X-ray crystallography, IR spectroscopy,
fluorescence spectra, and UV-vis absorption spectra. The com-
pound 1 crystallizes in Monoclinic, space group P2(1)/c with a =
8.2246(12), b = 11.5843(17), c = 15.005(2), α = 90◦, β = 94.218(2)◦,
γ = 90◦. In the anion [Cu2I4]2−, each Cu center is triangularly
coordinated by two µ2-I(2) atoms and one terminal I(1) atom. The
organic cationic [btx]2+ existed around it through supramolecular
interactions.
EXPERIMENTAL
Material and Measurement
All chemicals and solvents are of A.R. grade and used with-
out further purification. The dication btx·Cl2 is prepared as the
chloride salt by direct alkylation of dibenzyl chloride with tri-
ethylamine (acetonitrile served as the solvent).[16] Photolumi-
nescent measurement of [btx]Cu2I4 and the cation btx·Cl2 are
conducted on a Hitachi F-4500 spectrophotometer (Japan) and
Keywords binuclear coordination compound, organoammonium
cations, photoluminescent properties, self-assembly, UV-
vis absorption spectra
INTRODUCTION
The intelligent choice of transition-metal clusters and the data were collected at room temperature. The UV-vis spectra
organoammonium cations (OACs) may yield inorganic-organic were measured on a HP-8453 UV-visible spectrophotometer at
supramolecular systems with intriguing structural topologies room temperature. The IR spectrum was recorded on a Shimazu
and desirable properties.[1–5] Self-assembly is one of the most IR435 spectrometer (Japan) as KBr disk (4000–400 cm−1).
efficient methods for the synthesis of transition metal com-
Synthesis of the Complex
plexes, and for their wide applications in biological systems,
porous materials, catalytic reactions, the nonlinear optical ma-
terials, and advanced materials.[6 –13] Most significantly, the
structural information from the organic template can be im-
printed on the final supramolecular frameworks.[14] The term
template effect was first used and defined at the beginning of
the sixties.[15] This may not only lead to new supramolecular
systems with high dimensionality, but also shed light on the
cluster coordination complex. Thereby, we chose the organic
cation btx·Cl2 as organic template and organic structural direc-
tion agent and inorganic functional building block to assemble
For [btx][Cu2I4] (1), a methanol solution of btx·Cl2 (0.038
g, 0.1 mmol) is added to a stirring colorless solution of CuI
(0.019 g, 0.01 mmol) dissolved in 3 mL DMF/H2O (vol-
ume ratio of 4:1) in the presence of excess KI (0.084 g, 0.5
mmol). White precipitation appears and DMF solution is con-
tinued to be added until the precipitation disappeared com-
pletely. The solution is then filtrated and slowly evaporated
in a vial placed in the dark at room temperature. White crys-
tals of [btx][Cu2I4] suitable for X-ray analysis are obtained
after three days. IR (KBr, cm−1): 3440(s), 2966(s), 2940(m),
1516(s), 1448(s), 1402(s), 1297(s), 1172(s), 1146(s), 1005(s),
813(s), 788(s), 682(s), 628(s), 571(m), 506(s), 454(m).
Received 17 March 2011; accepted 3 August 2011.
The authors gratefully acknowledge the financial support of The
National Science Foundation of China (No. 20671083).
Address correspondence to Yun-Yin Niu, Department of Chem-
istry, Zhengzhou University, Zhengzhou 450052, P. R. China. E-mail:
niuyy@zzu.edu.cn.
X-Ray Structural Determination
Crystallographic data for the title compound 1 was collected
at 293(2) K on a Bruker APEX-II area-detector diffractome-
ter (Germany) equipped with graphite-monochromatized Mo-
Ka radiation (λ = 0.71073 Å). Its structure was solved by
364

SYNTHESES, CRYSTAL STRUCTURES
365
TABLE 1
vent volatilized fast, but it did not easily form crystals when
solvent volatilized too slow. After repeated experiments, the
mixed solvent of DMF and methanol was the most appropriate.
(b) Temperature: Solvent evaporation method was less affected
by temperature because it was carried out at room temperature.
While sometimes it might bring some influence on the evapo-
ration of solvent owing to the seasonal temperature difference.
(c) Materials ratio: The materials’ ratio played a major role in
crystallizing of compound 1. The ratio of CuI and KI could
have influence on the growth environment of compound 1. (d)
Crystallization time: The results showed that as long as the ratio
of solvents was chosen suitably, the reaction time in a week had
not significantly influenced on the shape of crystals.
Crystal data and structure refinement for 1
Compound
1
Formula
Formula weight
Crystal system
Space group
a/Å
b/Å
C10H19CuI2N
470.60
Monoclinic
P 2(1)/c
8.2246(12)
11.5843(17)
15.005(2)
90
c/Å
α/◦
β/◦
94.218(2)
90
γ /◦
Crystal Structure
[btx][Cu2I4] 1
Volume/ A3
1425.7(4)
4
2.192
Z
Calculated density, Mgm−3
The structure of compound 1 belongs to monoclinic crys-
tal system with space group P2(1)/c. The crystal data and
bond length are shown in Tables 1 and 2, respectively. The
single-crystal X-ray diffraction analysis revealed that compound
1 consisted of cationic [btx]2+ as a structure-directing agent
and inorganic anions cluster [Cu2I4]2−. It belonged to dinu-
clear compounds. In the inorganic anions cluster [Cu2I4]2−, the
Cu(1) center is three-coordinated in a distorted triangle geom-
etry by two µ2-I(2) atoms and one terminal I(1) atom. The
organic cationic [btx]2+ existed around inorganic anions clus-
ter [Cu2I4]2− through supramolecular interactions. In the in-
organic anions cluster [Cu2I4]2−, Cu(1)-I(2)-Cu(1)#1- I(2)#1
formed a parallelogram geometry, which was made of Cu(1)-
I(2), Cu(1)-I(2)#1, Cu(1)#1-I(2), and Cu(1)#1-I(2)#1 four bonds
ranging from 2.5716(7) Å to 2.5947(7) Å. The bond angles
I(2)-Cu(1)-I(2)#1 and Cu(1)-I(2)#1-Cu(1)#1 were 119.20(3)◦
and 60.80(3)◦, respectively. Meanwhile, there is also a bond be-
tween two Cu atoms to form a metal-metal interaction with the
bond length Cu(1)-Cu(1)#1 2.6143(13) Å and the I(1)-Cu(1)-
Cu(1)#1 bond angle is 176.16(4)◦. It was showed that two ter-
minal I atoms and two metal Cu atoms were essentially in a
straight line (Figure 1).
µ, mm−1
F(000)
Crystal size, mm
Temperature/ K
Reflections collected
Independent reflections
Refinement method
5.832
884
0.31 × 0.10 × 0.08
296(2)
10431
2638
Full-matrix least-squares
on Fˆ2
Data / restraints / parameters
Goodness-of-fit on Fˆ2
2638 / 0 / 130
1.030
Final R indices [I>2sigma(I)]
R1 = 0.0276, wR2 =
0.0678
R indices (all data)
R1 = 0.0381, wR2 =
0.0737
0.681
−0.763
Largest peak
Hole(e. Å−3
)
direct methods and expanded using Fourier techniques. The non-
hydrogen atoms were refined with anisotropic thermal parame-
ters. The hydrogen atoms were assigned with common isotropic
displacement factors and included in the final refinement by
using geometrical constraints. The structures were refined with
full-matrix least-squares techniques on F2 using the SHELXTL-
97 program package.[17] Crystal data are summarized in detail
in Table 1. Selected bond lengths and bond angles are listed in
Table 2.
RESULTS AND DISCUSSION
Synthesis of Discussion
This dinuclear coordination compound was yielded by self-
assembly of btx·Cl2 as organic template and CuI; preparation
of the compound was mainly affected by several factors: (a)
Solvent: In the formation of the crystal, crystallization rate was
not identical because different solvent volatilized at different
speed. Polycrystal or microcrystal was easily formed when sol-
FIG. 1. Structure unit of the compound 1.

366
1
H.-J. DU ET AL.
TABLE 2
Selected bond distances (Å) and angles (◦) for compound 1
Cu(1)-I(1)
Cu(1)-I(2)#1
N(1)-C(1)
N(1)-C(5)
I(1)-Cu(1)-I(2)
I(2)-Cu(1)-I(2)#1
I(2)-Cu(1)-Cu(1)#1
Cu(1)-I(2)-Cu(1)#1
C(3)-N(1)-C(7)
N(1)-C(1)-C(2)
C(1)-N(1)-C(5)
C(6)-C(5)-N(1)
C(9)#2-C(10)-H(10)
2.4926 (8)
2.5947 (7)
1.517 (5)
1.525 (5)
123.12 (3)
119.20 (3)
60.04 (3)
60.80 (3)
111.6 (3)
115.5 (4)
111.2 (3)
115.7 (3)
119.6
Cu(1)-I(2)
Cu(1)-Cu(1)#1
N(1)-C(3)
2.5716 (7)
2.6143 (13)
1.526 (5)
1.531 (5)
117.63 (3)
176.16 (4)
59.17 (2)
108.5 (3)
107.9 (3)
109.3 (3)
107.9 (3)
119.5
N(1)-C(7)
I(1)-Cu(1)-I(2)#1
I(1)-Cu(1)-Cu(1)#1
I(2)#1-Cu(1)-Cu(1)#1
C(1)-N(1)-C(3)
C(7)-N(1)-C(5)
C(1)-N(1)-C(7)
C(7)-N(1)-C(5)
C(8)-C(9)-H(9)
N(1)-C(7)-H(7B)
108.4
In the whole structure, the inorganic anions cluster [Cu2I4]2−
and the organic cationic [btx]2+ constituted a 2D planar struc-
ture, and both of them mutually filled their gaps through each
other. The organic cationic [btx]2+ played roles of balance
charge and filling agent in this structure (Figure 2).
There were C-H···I and C-H···Cu interactions between I and
Cu atoms of each inorganic anions cluster [Cu2I4]2− and hydro-
gen atoms of organic cations [btx]2+ (Figure 3). Via these weak
interactions and static electricity interactions, each formed unit
assembled to form the infinite spatial structure (Figure 4).
emission bandwidths are set at 5 nm. The spectra of complex
and organic cation at room temperature are illustrated in
Figure 5. The organic cation emits at 289 nm under excitation
at 256 nm. In contrast, compound 1 gives fluorescence center at
463 nm under excitation at 300 nm. Compared with the organic
cation a red shift of 174 nm in compound 1 has been observed,
which is considered to mainly arise from metal to ligand charge
transition (MLCT) inferred in some literature.[18] The results
here suggest that compound 1 is a potential candidate for
photoactive materials.
UV-Vis Absorption Spectra of btx·Cl2 and 1
Photoluminescent Properties
The UV-vis absorption spectra of organic cation btx·Cl2 in
methanol solution and compound 1 in DMF solution are shown
in Figure 6. The electronic spectra of cation btx·Cl2 showed
strong peak at 220 nm and weak peak at 267 nm. These peaks
are probably dominated by the π→π∗ transition. However, in
The fluorescence spectra of the complexes and organic cation
in solid state are recorded using a Hitachi F-4500 (fluorescence
spectrophotometer) in a 1 cm quartz cell. The excitation and
FIG. 2. 2D planar structure of compound 1.
FIG. 3. Interaction diagram of the compound 1.

SYNTHESES, CRYSTAL STRUCTURES
367
FIG. 4. Packing interaction diagram of the compound 1.
FIG. 5. (a) Photoluminescent spectra of the free cation btx·Cl2 in solid state at room temperature. (b) Photoluminescent spectra of compound 1 in solid state at
room temperature.

368
H.-J. DU ET AL.
FIG. 6. (a) UV-vis spectrogram for the methanol solution of organic cation btx·Cl2. (b) UV-vis spectrogram for the DMF solution of compound 1.
the spectra of compound 1 showed three peaks at 204 nm,
228 nm, and 265 nm, which probably arose from the π→π∗
transition. These absorption peaks appeared weak red shift due
to the different solvents.
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