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含环金属化氮杂环卡宾的发光有机金(III)配合物:合成、表征、电化学及光物理研究

Luminescent cyclometalated N-heterocyclic carbene-containing organogold(III) complexes: synthesis, characterization, electrochemistry, and photophysical studies.

作者信息

Au Vonika Ka-Man, Wong Keith Man-Chung, Zhu Nianyong, Yam Vivian Wing-Wah

机构信息

Centre for Carbon-Rich Molecular and Nano-Scale Metal-Based Materials Research and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong.

出版信息

J Am Chem Soc. 2009 Jul 1;131(25):9076-85. doi: 10.1021/ja9027692.

DOI:10.1021/ja9027692
PMID:19485381
Abstract

A new class of luminescent mononuclear and dinuclear N-heterocyclic carbene-containing gold(III) complexes has been synthesized and characterized. The X-ray crystal structures of most of the complexes have also been determined. Electrochemical studies reveal a ligand-centered reduction originated from the RC--N--CR moieties with no oxidation waves. Interestingly, one of the dinuclear complexes exhibited two distinct reduction couples instead of one with the first reduction occurring at less cathodic potential, probably related to the splitting of the pi* orbital-based LUMO resulting from intramolecular pi-pi interaction. The electronic absorption and luminescence behaviors of the complexes have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the intraligand pi-pi* transition, with mixing of a charge transfer character from the aryl ring to the pyridine moiety of the cyclometalating RC--N--CR ligand. The low-energy emission bands are ascribed to origins mainly derived from the intraligand pi-pi* states with an aryl to pyridine charge transfer character of the cyclometalating RC--N--CR ligand.

摘要

一类新型含氮杂环卡宾的单核和双核金(III)发光配合物已被合成并表征。大多数配合物的X射线晶体结构也已确定。电化学研究表明,还原反应以配体为中心,源于RC--N--CR部分,且无氧化波。有趣的是,其中一种双核配合物表现出两个不同的还原偶,而非一个,首次还原发生在较低的阴极电位,这可能与分子内π-π相互作用导致的基于π轨道的最低未占分子轨道(LUMO)分裂有关。还研究了这些配合物的电子吸收和发光行为。在室温下的二氯甲烷溶液中,低能量吸收带被指定为配体内π-π跃迁,伴随着从芳环到环金属化RC--N--CR配体吡啶部分的电荷转移特征混合。低能量发射带主要归因于配体内π-π*态的起源,具有环金属化RC--N--CR配体从芳基到吡啶的电荷转移特征。

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