Luminescent dinuclear copper(I) halide complexes double bridged
by diphosphine ligands: Synthesis, structure characterization, properties
and TD-DFT calculations
Xiayi Zhang
a
, Li Song
b
, Mingwei Hong
a
, Hongsheng Shi
a
, Kaijie Xu
a
, Qizhong Lin
a
, Yi Zhao
a
,
Yuan Tian
a
, Jiafeng Sun
a
, Kangying Shu
a
, Wenxiang Chai
a,c,
⇑
a
College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, PR China
b
Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Education Ministry, Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018,
PR China
c
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China
article info
Article history:
Received 3 May 2014
Accepted 13 July 2014
Available online 1 August 2014
Keywords:
Luminescence
Copper(I) halide complex
Diphosphine ligand
X-ray crystal structure
(TD-)DFT calculation
abstract
Four luminescent copper(I) halide complexes of the type [CuXPh
2
P(CH
2
)
n
PPh
2
][X=I,n =4 (1), 5 (2);
X = Br, n =4(3), 5 (4)] were prepared by reacting CuX with the appropriate diphosphine in a 1:1 M ratio.
All the complexes were characterized by spectroscopic analysis (IR, UV–Vis), elemental analysis and pho-
toluminescence studies. Single-crystal X-ray diffraction revealed that 1 and 2 are both dinuclear struc-
tures which are constructed by two
l
-I bridges and, especially, two diphosphine ligands as
l
2
bridges.
The copper(I) iodide complexes are thermally stable, and 2 melts at 242 °C. All the complexes exhibit a
strong emission in the solid state. The excited states have been assigned as a halide-to-ligand charge
transfer (XLCT) state mixed with a small amount of a metal-to-ligand charge transfer (MLCT) transition,
based on the TD-DFT calculations. The calculated electronic transitions have also been compared with the
experimental absorption spectra to understand the reason why there is some blue-shift of the low-energy
band when the halide atom changes from iodine to bromine, and an even greater blue-shift when the
ligand changes from DPPP to DPPB.
Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction
Highly luminescent transition metal complexes are widely
studied due to their broad applications in organic electrolumines-
cence (OEL) [1], solar energy conversion [2], light-driven fuel pro-
duction [3,4], photochemical catalysis [5], luminescence-based
sensors [6] and probes of biological systems [7]. Each of these
applications imposes specific demands on the materials, such as
chemical or electrochemical stability, color and color purity of
the emitted light, high emission quantum yield, specific emission
decay time and so on [8]. For instance, cyclometallated d
6
and d
8
complexes of the third row transition series, especially iridium(III),
have been employed in OEL products because of their high phos-
phorescence quantum yield, wavelength tenability and thermal
stability [9]. However, the use of these materials inevitably
involves other inherent questions, such as high cost, limited avail-
ability and toxicity of the precious metals [10]. In view of these
disadvantages, there is considerable interest in developing
luminescent complexes of the abundant, cheap and non-toxic
metal, copper [11].
Previously, there have been numerous studies on copper(I)
complexes, focusing on either their structural chemistry or their
luminescence. The first important system is [Cu(NN)
2
]
1+
complexes
which present luminescence that is markedly dependent on the
nature of the ligands. Some systematic studies have reported that
the luminescence originates from an MLCT excited state, and the
major non-radiative decay for the MLCT state is related to two
structural distortions of flattening and rocking due to the Jahn–
Teller effect of copper(II) [7,12]. In order to inhibit these distor-
tions, bulky substituents have been introduced into the phenan-
throline ligand at the 2,9-positions, and this method has been
proved to be useful in improving the luminescent quantum yield.
Similarly, the heteroleptic [Cu(NN)P
2
]
1+
complexes with sterically
crowded ligands, such as [Cu(dbp)(POP)]
1+
, also show a high lumi-
nescent yield [13]. The other one important structure is tetranu-
clear cube-like copper(I) halide clusters, [CuXL]
4
(X = halogen,
L = pyridine or phosphine ligand), which shows not only strong
http://dx.doi.org/10.1016/j.poly.2014.07.034
0277-5387/Ó 2014 Elsevier Ltd. All rights reserved.
⇑
Corresponding author at: College of Materials Science and Engineering, China
Jiliang University, Hangzhou 310018, PR China. Tel.: +86 0571 86835738.
E-mail address: wxchai@cjlu.edu.cn (W. Chai).
Polyhedron 81 (2014) 687–694
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
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