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通过超分子自组装构建发光的双核双环金属化金(III)炔基及其溶剂依赖性形态。

Luminescent Dinuclear Bis-Cyclometalated Gold(III) Alkynyls and Their Solvent-Dependent Morphologies through Supramolecular Self-Assembly.

机构信息

Institute of Molecular Functional Materials, Areas of Excellence Scheme, University Grants Committee (Hong Kong) and, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.

Department of Chemistry, South University of Science and Technology of China, Shenzhen, Guangdong, 518055, P. R. China.

出版信息

Chemistry. 2016 Nov 2;22(45):16258-16270. doi: 10.1002/chem.201603186. Epub 2016 Sep 28.

Abstract

A series of luminescent bis-cyclometalated gold(III) complexes containing bridging alkynyl ligands of different natures has been synthesised and characterised. The photophysical properties of the complexes have been investigated through electronic absorption spectroscopy and emission studies. The vibronic emission bands are found to originate from the triplet intraligand (IL) π-π* excited states of the bis-cyclometalating ligands with some mixing of IL π-π* character of the alkynyl ligands. The electrochemical study of a nonsymmetric dinuclear complex shows two successive reduction processes originating from the reductions of the two different cyclometalating ligands. The complexes are found to undergo supramolecular self-assembly processes driven by π-π stacking and hydrophobic/hydrophilic interactions to give honeycomb nanostructures, as revealed from the SEM images. Solvent-dependent morphological transformations have also been observed, which have been studied by SEM and H NMR spectroscopy.

摘要

已合成并表征了一系列含有不同性质桥联炔基配体的发光双环金属化金(III)配合物。通过电子吸收光谱和发射研究研究了配合物的光物理性质。发现带系发射源于双环金属化配体的三重态内配体(IL)π-π激发态,其中一些混合了炔基配体的 IL π-π特征。非对称双核配合物的电化学研究表明,两个连续的还原过程源于两个不同的环金属化配体的还原。从 SEM 图像可知,这些配合物通过π-π 堆积和疏水/亲水相互作用进行超分子自组装,形成蜂窝状纳米结构。还观察到溶剂依赖性形态转变,通过 SEM 和 H NMR 光谱对其进行了研究。

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