蔷薇红素的铜络合作用：双铜蔷薇红素和单铜线性三联二吡咯配合物的形成。

Copper complexation of rosarin: formation of bis-copper rosarin and mono-copper linear tridipyrrin complexes.

作者信息

Lv Xiaojuan, Qian Long, Tkachenko Nikolay V, Zhang Tao, Qiu Fengxian, Aratani Naoki, Ikeue Takahisa, Pan Jianming, Xue Songlin

机构信息

School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China.

Department of Chemistry, University of California, Berkeley, CA 94720, USA.

出版信息

Dalton Trans. 2024 Oct 22;53(41):16879-16884. doi: 10.1039/d4dt02161d.

DOI:10.1039/d4dt02161d

PMID:39360845

Abstract

A novel rosarin di-Cu complex 2Cu-1 and a linear six-pyrrolic mono-copper complex 1Cu-1 were synthesized using rosarin as the ligand. The molecular conformations of these complexes were confirmed by X-ray crystallography. The optical study of 1Cu-1 indicated NIR-II absorption due to the long six-pyrrolic ligand and the ICT effect. The 2Cu-1 complex exhibited a very narrow electronic reduction-oxidation gap of 0.50 eV, attributed to the antiaromatic characteristics of the rosarin ring. The first HER study of the di-copper rosarin complex 2Cu-1 indicated that the multi-metal poly-pyrrolic complexes are promising molecular hydrogen evolution reaction catalysts.

摘要

以玫瑰红素为配体合成了一种新型玫瑰红素二铜配合物2Cu-1和一种线性六吡咯单铜配合物1Cu-1。这些配合物的分子构象通过X射线晶体学得到证实。对1Cu-1的光学研究表明，由于长的六吡咯配体和分子内电荷转移（ICT）效应，其具有近红外二区吸收。2Cu-1配合物表现出非常窄的0.50 eV的电子还原-氧化能隙，这归因于玫瑰红素环的反芳香特性。对二铜玫瑰红素配合物2Cu-1的首次析氢反应（HER）研究表明，多金属聚吡咯配合物是很有前景的分子析氢反应催化剂。