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一种合成用于细胞内缺氧成像的邻碳硼烷功能化磷光铱(III)配合物的简便方法。

A Convenient Approach To Synthesize o-Carborane-Functionalized Phosphorescent Iridium(III) Complexes for Endocellular Hypoxia Imaging.

作者信息

Li Xiang, Tong Xiao, Yan Hong, Lu Changsheng, Zhao Qiang, Huang Wei

机构信息

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, P.R. China.

Key Laboratory for Organic Electronics and Information Displays and Institute of Advanced Materials, Nanjing University of Posts and Telecommunications, Nanjing, 210023, P.R. China.

出版信息

Chemistry. 2016 Nov 21;22(48):17282-17290. doi: 10.1002/chem.201603340. Epub 2016 Oct 27.

DOI:10.1002/chem.201603340
PMID:27786384
Abstract

The structure-property relationship of carborane-modified iridium(III) complexes was investigated. Firstly, an efficient approach for the synthesis of o-carborane-containing pyridine ligands a-f in high yields was developed by utilizing stable and cheap B H (Et N) as the starting material. By using these ligands, iridium(III) complexes I-VII were efficiently prepared. In combination with DFT calculations, the photophysical and electrochemical properties of these complexes were studied. The hydrophilic nido-o-carborane-based iridium(III) complex VII showed the highest phosphorescence efficiency (abs. ϕP =0.48) among known water-soluble homoleptic cyclometalated iridium(III) complexes and long emission lifetime (τ=1.24 μs) in aqueous solution. Both of them are sensitive to O , and thus endocellular hypoxia imaging of complex VII was realized by time-resolved luminescence imaging (TRLI). This is the first example of applying TRLI in endocellular oxygen detection with a water-soluble nido-carborane functionalized iridium(III) complex.

摘要

研究了碳硼烷修饰的铱(III)配合物的结构-性质关系。首先,以稳定且廉价的BH(EtN)为起始原料,开发了一种高产率合成含邻碳硼烷吡啶配体a-f的有效方法。通过使用这些配体,高效制备了铱(III)配合物I-VII。结合密度泛函理论计算,研究了这些配合物的光物理和电化学性质。亲水性巢式邻碳硼烷基铱(III)配合物VII在已知的水溶性均配环金属化铱(III)配合物中显示出最高的磷光效率(绝对ϕP = 0.48),并且在水溶液中的发射寿命长(τ = 1.24 μs)。它们两者对O均敏感,因此通过时间分辨发光成像(TRLI)实现了配合物VII的细胞内缺氧成像。这是将TRLI应用于水溶性巢式碳硼烷官能化铱(III)配合物进行细胞内氧检测的首个实例。

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