Synthesis, Crystal Structure and Luminescent Properties of A Dinuclear Copper(I) Complex Containing 2,9-di-n-butyl-1,10-phenanthroline

LIU Wen-song; REN Hong-yang; LI Xiang-qi; WANG Bing-xi

doi:10.3788/fgxb20123312.1277

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Synthesis, Crystal Structure and Luminescent Properties of A Dinuclear Copper(I) Complex Containing 2,9-di-n-butyl-1,10-phenanthroline

更新时间：2020-08-12

- Synthesis, Crystal Structure and Luminescent Properties of A Dinuclear Copper(I) Complex Containing 2,9-di-n-butyl-1,10-phenanthroline
- Chinese Journal of Luminescence Vol. 33, Issue 12, Pages: 1277-1282(2012)
- 作者机构：
  
  福州大学材料科学与工程学院,福建福州,350108
- 作者简介：
- 基金信息：
- DOI：10.3788/fgxb20123312.1277
  CLC： O614.1
- Received：09 August 2012，
  
  Revised：23 September 2012，
  
  Published：10 December 2012
- 稿件说明：
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刘文崧, 任泓扬, 李湘祁, 王炳喜. 2,9-二正丁基-1,10-菲咯啉双核铜(I)配合物的合成、晶体结构及光学性质[J]. 发光学报, 2012,33(12): 1277-1282

LIU Wen-song, REN Hong-yang, LI Xiang-qi, WANG Bing-xi. Synthesis, Crystal Structure and Luminescent Properties of A Dinuclear Copper(I) Complex Containing 2,9-di-n-butyl-1,10-phenanthroline[J]. Chinese Journal of Luminescence, 2012,33(12): 1277-1282
刘文崧, 任泓扬, 李湘祁, 王炳喜. 2,9-二正丁基-1,10-菲咯啉双核铜(I)配合物的合成、晶体结构及光学性质[J]. 发光学报, 2012,33(12): 1277-1282 DOI： 10.3788/fgxb20123312.1277.

LIU Wen-song, REN Hong-yang, LI Xiang-qi, WANG Bing-xi. Synthesis, Crystal Structure and Luminescent Properties of A Dinuclear Copper(I) Complex Containing 2,9-di-n-butyl-1,10-phenanthroline[J]. Chinese Journal of Luminescence, 2012,33(12): 1277-1282 DOI： 10.3788/fgxb20123312.1277.

摘要

以2

9-二正丁基-1

10-菲咯啉(dnbp)和碘化亚铜为原料

在四氢呋喃溶液中反应合成了一种新型中性双核铜(Ⅰ)配合物[CuI(dnbp)]

。采用X射线单晶衍射、核磁共振氢谱、紫外-可见吸收光谱表征其结构

荧光光谱测定其发光性能。结果表明:该配合物分子由两个Cu(Ⅰ)离子通过两个碘离子桥联形成畸变的菱形Cu

核心和dnbp螯合配体构成

配合物中I—Cu—I的夹角较小(106.08°)

两个Cu(Ⅰ)离子的距离很长(0.319 4 nm)

表明它们的相互作用可以忽略。上述结构的特征主要由dnbp配体大的空间位阻造成。配合物晶体属于三方晶系

空间群为

-3

晶胞参数

=4.404 14(11) nm

= 4.404 14(11) nm

=1.085 92(4) nm

=120°

=18.241 1(9) nm

。配合物在二氯甲烷溶液中出现350~500 nm的吸收峰

归属于金属离子到配体的电荷转移跃迁(MLCT)。室温下

当激发波长为365 nm时

其最大发射波长为653 nm

发光寿命为3.1 μs

光致发光量子产率为0.013。发光机制属于金属离子和卤素到配体电荷转移激发态的磷光发射。低温下

配合物最大发射波长蓝移至645 nm

发射峰变窄。

Abstract

A new neutral dinuclear copper(Ⅰ) complex bearing N-ligands 2

9-di-n-butyl-1

10-phenanthroline (dnbp)

[CuI(dnbp)]

was synthesized by the reaction of CuI and dnbp in tetrahydrofuran solution. The complex was characterized by single crystal X-ray diffraction

H NMR

UV-Vis spectra

and photoluminescence spectra. The results show that the complex consists of a distorted tetrahedral Cu

core

in which two copper(Ⅰ) ions are linked by two iodo-bridges

and two dnbps chelated with copper(Ⅰ) ions

respectively. The complex shows small angle of I—Cu—I (106.08°)

and long Cu…Cu distance (0.314 9 nm) which suggests a negligible interaction between two copper ions. These features can be attributed to the bulk steric hindrance of dnbp ligands. The complex belongs to trigonal system with space group of

-3 and cell dimensions

= 4.404 14(11) nm

=1.085 92(4) nm

= 120°

=18.241 1(9) nm

. The complex has a low-energy absorption band ranging from 350 nm to 500 nm in dichloromethane solution

which can be assigned to the metal-to-ligand charge transfer (MLCT) transitions. At room temperature

the complex in the solid state exhibits red photoluminescence with a broad emission band from 550 nm to 800 nm and the maximum peak at 653 nm under excitation at 365 nm. The emission lifetime of the complex is 3.1 μs

and photoluminescence quantum yield is 0.013. The luminescence mechanism of the complex belongs to the phosphorescent emission at the exited state

which is formed by electron charge transition from cuprous ion and halogen to ligand dnbps. At 10 K

the maximum emission peak shifts to 645 nm with narrow spectral band width.

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Keywords

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