发光卤化铜（I）双核配合物：合成、结构与TD-DFT计算

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"发光的双核配体双桥连接的卤化双核铜（I）配合物：合成，结构表征，性质和TD-DFT计算" 本文详细介绍了四类具有发光特性的双核铜（I）卤化物配合物，它们的化学式为[CuXPh2P（CH2）（n）PPh2]，其中X代表卤素（I或Br），n为4或5。这些配合物是通过将CuX与相应的二膦配体以1:1摩尔比例反应制得的。通过对这些配合物进行多种表征技术，包括红外光谱（IR）、紫外-可见光谱（UV-Vis）、元素分析和光致发光研究，研究人员得以深入理解它们的结构和性质。单晶X射线衍射分析揭示了1号和2号配合物的双核结构，两个配体通过μ-I桥连接，形成一个独特的112桥模式。碘化铜（I）配合物显示出了良好的热稳定性，其中1号配合物在242摄氏度下熔化。在固态下，所有配合物都展现出强烈的发射特性，这表明它们在光致发光应用中有潜在价值。为了进一步探究这些配合物的发光性质，研究人员进行了时间依赖的密度泛函理论（TD-DFT）计算。计算结果表明，激发态是卤化物-配体电荷转移（XLCT）状态与少量金属到配体的电荷转移（MLCT）状态的混合。通过对计算出的电子跃迁与实验吸收光谱的比较，揭示了当卤原子从碘变为溴时，低能带出现蓝移的现象，同时，当配体发生改变（如DPPP更改为DPPB）时，蓝移程度更大。这些发现揭示了卤素类型和配体结构对配合物光谱性质的影响。这些发光卤化铜（I）配合物的合成、结构分析以及TD-DFT计算提供了深入理解其光学性能的宝贵信息，对于设计新型发光材料和优化其光物理性质具有重要意义。这些研究对于开发应用于照明、显示技术以及传感器等领域的高性能铜（I）配合物具有指导作用。

Luminescent dinuclear copper(I) halide complexes double bridged

by diphosphine ligands: Synthesis, structure characterization, properties

and TD-DFT calculations

Xiayi Zhang

, Li Song

, Mingwei Hong

, Hongsheng Shi

, Kaijie Xu

, Qizhong Lin

, Yi Zhao

Yuan Tian

, Jiafeng Sun

, Kangying Shu

, Wenxiang Chai

a,c,

⇑

College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, PR China

Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Education Ministry, Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018,

PR China

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

P(CH

)

PPh

][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

-I bridges and, especially, two diphosphine ligands as

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.

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

and d

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)

]

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

]

complexes with sterically

crowded ligands, such as [Cu(dbp)(POP)]

, also show a high lumi-

nescent yield [13]. The other one important structure is tetranu-

clear cube-like copper(I) halide clusters, [CuXL]

(X = halogen,

L = pyridine or phosphine ligand), which shows not only strong

http://dx.doi.org/10.1016/j.poly.2014.07.034

⇑

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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