Luminescent monomeric and polymeric cuprous halide complexes with 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene as ligand

Article abstract of DOI:10.1016/j.inoche.2015.06.014

Abstract Reaction of cuprous bromide with equimolar amounts of 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene (dpb) affords a mononuclear three-coordinated complex [CuBr(dpb)] (F2) with dpb acting as a chelating ligand. In contrast, using cuprous iodide

Full text of DOI:10.1016/j.inoche.2015.06.014

Luminescent Monomeric and Polymeric Copper(I) Halides Complexes with
1,2-Bis(3,5-dimethylpyrazol-1-ylmethyl)- Benzene as Ligand
Fengshou Wu, Hongbo Tong, Kai Wang, Jie Zhang, Zebin Xu, Xunjin
Zhu
PII:
DOI:
Reference:
S1387-7003(15)00235-X
doi: 10.1016/j.inoche.2015.06.014
INOCHE 6019
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
6 May 2015
9 June 2015
13 June 2015
Please cite this article as: Fengshou Wu, Hongbo Tong, Kai Wang, Jie Zhang, Zebin Xu,
Xunjin Zhu, Luminescent Monomeric and Polymeric Copper(I) Halides Complexes with
1,2-Bis(3,5-dimethylpyrazol-1-ylmethyl)- Benzene as Ligand, Inorganic Chemistry Commu-
nications (2015), doi: 10.1016/j.inoche.2015.06.014
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ACCEPTED MANUSCRIPT
Luminescent Monomeric and Polymeric Copper(I) Halides
Complexes with 1,2-Bis(3,5-dimethylpyrazol-1-ylmethyl)-
Benzene as Ligand
Fengshou Wu, a,b Hongbo Tong,d Kai Wang,a* Jie Zhang,c* Zebin Xu,a and Xunjin Zhu, b*
a Key Laboratory for Green Chemical Process of the Ministry of Education, Wuhan Institute of
Technology, Wuhan, P. R. China.
b Department of Chemistry, Hong Kong Baptist University, Hong Kong, P. R. China.
c School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou, P. R. China.
d Institute of Applied Chemistry, Shanxi University, Taiyuan, P. R. China.
*Corresponding author. Fax: (+86) 027-87194980. Tel: (+86) 027-87446971.
E-mail: (K.W): kaiwang@wit.edu.cn; (J. Z): zhang_jie@tzc.edu.cn; (X.Z): xjzhu@hkbu.edu.hk.
ABSTRACT:
Reaction
of
copper(I)
bromide
with
equimolar
amounts
of
1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene (dpb) afforded a mononuclear three-coordinated
complex [CuBr(dpb)] (F2) with dpb acting as a chelating ligand. In contrast, copper(I) iodide
under the same conditions gave the polymeric compound [Cu2I2(dpb)]n (F1) which contains
1
double-bridging iodine atoms. The complexes were characterized by element analysis and H
NMR spectroscopy, and the crystal structures were determined by single-crystal X-ray diffraction
methods. The Cu(I) complexes are luminescent in the solid state at ambient temperature. Intense
orange emission for complex F1 is observed, with maxima at 593 nm, probably ascribed to a
combination of a halide-to-metal charge transfer and copper-centered d→s, p transitions. F2
exhibits a blue photoluminescence, with emission maximum at 515 nm, assigned to
metal-to-ligand charge-transfer excited states, probably mixed with some halide-to-ligand
characters.
Key Words: Cu(I) halides, luminescence, crystal structures, coordination polymers
Copper(I) complexes have attracted considerable interest because of their rich structural and
photophysical properties [1] and potential applications as inexpensive, abundant materials in

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optoelectronics [2], catalysis [3], and biological systems [4]. Copper(I) halide aggregates
constitute a large family of compounds studied mainly for their photochemical and photophysical
properties [5] which are at the forefront of coordination chemistry and crystal engineering
research [6]. To date, a large number of mono- and polynuclear copper(I) halides with various
aggregates, such as rhomboid dimer, cubane tetramer, stepped cubane tetramer, open cubane
tetramer and diamondoid tetramer have been synthesized by self-assembly reactions [7]. This
variability arises from the many possible combinations of coordination numbers (two, three and
four) available for copper(I) and geometries that can be adopted by the halide ions (from terminal
to μ2- and up to μ8- bridging) [8].
Based on our earlier observations on a series of copper (I) chain polymers and dimeric complex
[9], the coordination behavior (terminal or bridging mode) has been supposed to depend on the
nature of the halide ligand. In particular, formation of halide bridges has been found to be favored
for the “soft” iodide but not for the “harder” chloride ligands, whereas both bridging and terminal
bonding modes were observed for the bromide ligands since bromide lies on the borderline
between soft and hard bases [10]. The luminescent properties of copper(I) halide aggregates have
been extensively studied by Ford et al., who showed that luminescent behaviour and geometries of
the aggregate are strictly related [11]. Among the various clusters acting as connecting nodes,
dimeric and tetrameric units have been seen to be the most common. In the case of the cluster
Cu4I4py4, the emissions have been assigned to XLCT (halide to ligand charge-transfer) and CC
(cluster-centered) excited states on the basis of experimental and theoretical studies [12]. Herein,
we report the preparation, crystal structures and photophysical properties of two novel
coordination compounds, namely [Cu2I2(dpb)]n (F1) and [CuBr(dpb)] (F2), formed upon reacting
copper(I) halides with 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene (dpb) [13] in toluene.
Both of the two complexes are photoluminescent in the solid state, and the emissive properties of
the complexes are very dependent on their structures.
The ligand and Cu(I) complexes were prepared according to the literature method with minor
revisions [14]. As shown in Scheme 1, 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene was
synthesized by condensing of 1,2-bis(bromomethyl) benzene with two equivalent of
3,5-dimethylpyrazole through a phase-transfer catalyzed reaction. Subsequently, the reactions of
Cu(I) halides with dpb in dry toluene afforded the corresponding Cu(I) complexes in good yields.

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The analytically pure Cu(I) complexes were obtained by further purification through precipitation
and washing steps. The complexes are stable in the atmosphere in the solid state, but will be
oxidized by several days’ air exposure in solution. The ligand and Cu(I) complexes were
characterized by 1H NMR, elemental analysis and MALDI-TOF spectroscopy.
The crystals of F1 and F2 suitable for X-ray diffraction analysis were obtained by diffusion of
hexane into the dichloromethane solution of the complexes and both of them were characterized
by crystallographic analyses. Perspectives views of F1 and F2 are shown in Fig.1 and Fig.2,
respectively. The crystallographic data of the complexes are given in Table 1. Remarkably, the
single crystal structures of the complexes significantly depend on the cuprous halides used for
coordination. As shown in Fig.2, treatment of equimolar quantities of cuprous bromide and
1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene in dry toluene solution affords a monomeric
complex [CuBr(dpb)] (F2). The three-coordinated Cu(I) atom was surrounded by two nitrogen
atoms from one dipyrazole ligand, and one bromide to generate a trigonal configuration with the
N3-Cu-N1, N3-Cu-Br and N1-Cu-Br angles falling in the range of 115.47(9) o to 124.57(10)o. The
Cu-Br distance is 2.3472 Å, which is shorter than that of four-coordinated Cu(I) bromide
complexes (2.5369 Å) [10], but a slightly longer than that of two-coordinated complex (2.2012 Å)
[9], probably attributed to the steric hindrance around Cu center. The Cu-N bond lengths of the
complex localize in a region of 2.007-1.973 Å, which are comparable to the literature values [15].
In contrast, reaction of cuprous iodide under the same experimental conditions displays a very
different coordination mode, where two dipyrazole ligands were bridged by a rhombus Cu2I2 to
afford a 1-D linear coordination polymer [Cu2I2(dpb)]n (F1), as shown in Fig.1. The copper and
μ2-iodide ions each occupy the opposite corners of the distorted square plane (Cu2I2), which
displays a much closer Cu1-Cu2 distance (2.565 Å), much separated I1-I2 distance (4.472 Å),
Cu1-I1 2.568(6) Å, I1-Cu1-I2 120.61(2)°, and Cu1-I1-Cu2 59.225(17)°. It should be noted that the
relatively short Cu1-Cu2 distance in F1 is less than twice the van der Waals radius (1.4 Å) of
Cu(I), implying a strong metal-metal interaction may exist between the two Cu atoms [16]. The
phenomenon of Cu-Cu interaction has been extensively observed for Cu4I4 clusters and other
multinuclear Cu(I) complexes [9, 17].
The UV–vis absorption spectra of the Cu(I) complexes in CH2Cl2 solution at room temperature
are shown in Fig.3. Both of F1 and F2 display intense absorption bands around 250 nm, which can

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be attributed to the π-π* transitions inside the dipyrazole ligand [1a]. In addition, the complexes
display additional bands between 200 and 350 nm, which can be assigned to the low-lying
metal-to-ligand charge-transfer (MLCT) bands involving mainly the 3d orbitals of Cu(I) and the
unoccupied π* orbital of the dipyrazole ligand, probably mixed with some halide-to-ligand
charge-transfer (XLCT) character [18].
The photoluminescence properties of the complexes in the solid state were recorded at ambient
temperature. Upon exposure to UV radiation, F1 exhibits an orange luminescence, and a broad
emission spectrum was observed with the maximum located at 593 nm, as shown in Fig.4. F2
emits an intense blue light under UV irradiation with maximum peak at 515 nm. The distinct
photoluminescence behaviors of the cuprous halide complexes are probably attributed to their
different crystal structures. According to the previous papers [19], the excited states in Cu(I)
halide complexes possibly include ligand-based (π-π*), metal-to-ligand charge transfer (MLCT),
halogen-to-ligand charge transfer (XLCT) and cluster-centered (CC). Since F1 shows a strong
interaction between the two Cu atoms, the photoluminescence of F1 could be attributed to a
combination of a halide-to-metal charge transfer (XMCT) and copper-centered d→s, p transitions
(3CC). The crystal structure of F2 indicates no Cu–Cu interactions. Accordingly, the
photoluminescence of F2 was assigned to the transition from the dπ orbital (3d10) of the Cu center
to the unoccupied π* orbital of the dipyrazole ligand, probably mixed with some XLCT character
[20]. Besides, the microsecond lifetime scale of the emitting species implies that the transitions
may arise from the triplet excited states, as shown in Table 2.
The thermogravimetric analysis of the complexes was carried out in nitrogen atmosphere with a
heating rate of 15 °C min−1. As depicted in Fig.5, both of the two Cu (I) complexes have high
decomposition temperatures, with 10% weight loss up to 250 °C. On further hearting, a two-step
weight loss was observed for F2 between 250 and 900 °C, in which the first weight loss between
250 and 350 °C is assigned to the removal of dipyrazole ligand, and the second step in the range
350-900 °C corresponds to the gradually loss of bromide. As expected, the cuprous iodides
complex F1 containing Cu2I2 cluster show higher thermal stability than that of F2, with
decomposition temperature up to 268 °C.
In summary, the coordination behavior of Cu(I) bromide and iodide in the presence of
1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene (dpb) as ligand have been established.

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Single-crystal structure analyses revealed that two different types of compounds, namely,
monomeric with three-coordinated Cu(I) complex for X = Br (F2) and polymeric with
double-bridging iodo ligands for X = I (F1), have been isolated under the same reaction conditions.
The Cu-Cu distance of F1 (2.56 Å) is shorter than the sum of the van der Waals radii of copper(I)
(2.80 Å), indicating a strong metal-metal bonding interaction. The Cu(I) complexes are
luminescent in the solid state at ambient temperature. The blue and orange emitters obtained are
particularly interesting for OLED and OLEC applications. On the basis of this work, further
synthesis and structural and photophysical studies of novel heteronuclear coordination polymers
will be also underway in our laboratory.
Acknowledgment
This work was supported by the Project of Educational Commission of Hubei Province of China
(D20141506) and the Zhejiang Provincial Natural Science Foundation of China (No.
LQ13B010001).
Appendix. Supplementary material
CCDC-1054226 (F1) and CCDC-1054225 (F2) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this
article, including synthetic details of ligand and complexes, and excitation spectrum can be found
in the online version.
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[14] Synthesis of Cu(I) complexes. To a dry and degassed toluene (10 mL) solution of dpb (1
mmol) was added CuX (143.5 mg, 1 mmol). The mixture was kept at reflux under nitrogen
for 12 h. Upon cooling, a precipitate was formed. The solid was filtered off, washed with
toluene, diethyl ether and hexane and then recrystallised from dichloromethane/hexane (1: 3)
solution as white crystals. For F1, 1H NMR (400MHz, DMSO-d6): δ/ppm . 1 (s, , e -
pz), 2.27 (s, 6H, Me3-pz), 5.43 (s, 4H, CH2), 6.00 (s, 2H, H4-pz), 7.03-7.06 (m, 2H, H3,6-ph)
and 7.26-7.28 (m, 2H, H4,5-ph). Anal.Calcd for C18 H22 Cu2 I2 N4: C, 32.01; H, 3.28; N, 8.30.
1
Found: C, 33.87; H, 3.42; N, 8.45. For F2, H NMR (400MHz, DMSO-d6): δ/ppm .1 (s,
6H, Me5-pz), 2.36 (s, 6H, Me3-pz), 5.44 (s, 4H, CH2), 6.04 (s, 2H, H4-pz), 7.03-7.07 (m, 2H,
H3,6-ph) and 7.25-7.28 (m, 2H, H4,5-ph). Anal.Calcd for C18 H22 Br Cu N4: C, 49.38; H,
5.06; N, 12.80. Found: C, 50.24; H, 5.18; N, 13.25.
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Scheme 1. The synthetic routes for the Cu(I) halides complexes.
Fig.1. Perspective view of the structure of F1. Thermal ellipsoids are drawn at 50% probability
level. Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (°): Cu1-N1
1.975(3), Cu1-Cu2 2.5659(7), Cu1-I1 2.5687(6), Cu2-I1 2.6233(6), N1-Cu1-Cu2 175.90(9),
N1-Cu1-I1 121.68(9), Cu2-Cu1-I1 61.447(19), N1-Cu1-I2, 117.71(9), Cu2-Cu1-I2 59.251(18),
I1-Cu1-I2 120.61(2), N3-Cu2-I1, 114.99(9), Cu1-I1-Cu2 59.225(17), I2-Cu2-I1 119.88(2),
Cu2-I2-Cu1 60.104(18).

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Fig.2. Perspective view of the structure of F2. Thermal ellipsoids are drawn at 50% probability
level. Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (°): Cu-N1
2.007(3), Cu-N3 1.973(4), Cu-Br 2.3472(12), N3-Cu-N1 119.94(13), N3-Cu-Br 124.57(10),
N1-Cu-Br 115.47(9), N2-N1-Cu 123.2(3).
2.5
F1
F2
2.0
1.5
1.0
0.5
0.0
200
300
400
Wavelength (nm)
Fig.3. Absorption spectrum of Cu(I) complexes in DCM solution at room temperature.

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1.0
F1
F2
0.8
0.6
0.4
0.2
0.0
400
500
600
700
Wavelength (nm)
Fig.4. Emission spectra of Cu(I) complexes in the solid at room temperature.
100
F1
F2
80
60
40
20
0
200
400
T(C)
600
800
Fig.5. TGA traces of complexes F1 and F2.

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Table 1.Summary of Crystallographic Data
Parameter
Formula
F1
F2
C18 H22 Cu2 I2 N4 C18 H22 Br Cu N4
Fw
675.28
437.85
296(2)
0.71073
orthorhombic
Pna2(1)
14.387(6)
12.587(5)
10.200(5)
90.00
T (K)
296(2)
Radiation (λ, Å)
cryst syst
space group
a( Å )
0.71073
monoclinic
P2(1)/n
10.3576(8)
14.0032(10)
15.4409(11)
90.00
b ( Å )
c ( Å )
α(deg)
β (deg)
105.0690(10)
90.00
90.00
γ (deg)
V( Å3)
90.00
2162.5(3)
4
1847.0(14)
4
Z
ρcalcd (g cm-3)
absorption coefficient (mm-1)
F(000)
2.074
1.575
4.831
3.352
1288
888
crystal size (mm3)
θmin, θmax (deg)
limiting indices
0.36 x 0.33 x 0.33 0.35 x 0.25 x 0.24
2.00，25.05
-12 < h <12,
-14< k < 16,
-18 < l < 17
11874
2.15, 25.05
-17 < h < 17,
-10 < k < 14,
-11 < l < 12
9958
no. reflns collected
no. unique reflns
Rint
3835
3218
0.0315
0.0484
data/restr/params
GOOF on F2
final R1, wR2
[I > 2ó(I)] [a]
3835 / 0 / 240
1.019
3218/ 1/ 222
1.079
0.0282, 0.0584
0.0345, 0.0603
R1, wR2 (all data)
0.0390, 0.0624
0.0540, 0.0649
largest diff peak and hole (e•Å-3) 0.889 and -0.423 0.307 and-0.289
Flack number
0.105
[a] R1 = ΣFo Fc/ ΣFo. wR2 = [Σw(Fo   Fc2)2/ ΣwFo  ]
2
2 2 1/2

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Table 2. Photophysical and thermal properties of F1 and F2 at room temperature.
a
b
Complex
λabs
λem
(nm)
593
515
τ b (μs)
Tdecc (℃)
(nm)
F1
F2
250,300~340
250,300~340
13.6
5.2
268
250
a Measurements were done in 1 × 10-6 mol L-1 solution in
b
DCM at 298 K; Measured at the excitation of 300 nm in
powder; c Defined as the temperature of 10% weight loss.

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Graphical Abstract
The preparation, crystal structures and photophysical properties of two novel coordination
compounds, namely [Cu2I2(dpb)]n and [CuBr(dpb)], formed upon reacting copper(I) halides
with 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene (dpb) were reported. Both of the two
complexes are photoluminescent in the solid state, and their emissive properties are very
dependent on their structures.

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Highlights
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Two novel coordination compounds, namely [Cu2I2(dpb)]n and [CuBr(dpb)] were prepared
and characterized.
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
Crystal structures of the monomeric and polymeric Cu(I) halides complexes were presented.
The Cu(I) complexes are luminescent in the solid state at ambient temperature.