基于角联吡啶的手性分子正方形：自组装、表征及光物理性质

Chiral molecular squares based on angular bipyridines: self-assembly, characterization, and photophysical properties.

作者信息

Lee Suk Joong, Kim Jason S, Lin Wenbin

机构信息

Department of Chemistry, CB#3290, University of North Carolina, Chapel Hill, North Carolina 27599, USA.

出版信息

Inorg Chem. 2004 Oct 18;43(21):6579-88. doi: 10.1021/ic0497937.

DOI:10.1021/ic0497937

PMID:15476354

Abstract

Chiral molecular squares 1-12 based on M(dppe) metallocorners (M = Pd or Pt, and dppe = bis(diphenylphosphino)ethane) and new angular bipyridine bridging ligands derived from the 1,1'-binaphthyl framework were readily assembled and characterized by a variety of techniques including infrared, UV-vis, circular dichroism (CD), and NMR spectroscopy, and ESI mass spectrometry. All these chiral metallocycles are highly luminescent in solution at room temperature with quantum efficiency of 0.06-0.63. Interestingly, when equal molar enantiopure molecular squares of opposite handedness were mixed in solution, a new meso dimeric metallocycle with C(2) symmetry formed. This result indicates the lability of the M-pyridyl bonds in these metallocycles, which may hinder their applications in many enantioselective processes.

摘要

基于M(dppe)金属角（M = Pd或Pt，dppe = 双（二苯基膦基）乙烷）和源自1,1'-联萘骨架的新型角形联吡啶桥连配体的手性分子方块1 - 12易于组装，并通过包括红外、紫外可见、圆二色性（CD）、核磁共振光谱和电喷雾电离质谱在内的多种技术进行表征。所有这些手性金属环在室温下的溶液中都具有高发光性，量子效率为0.06 - 0.63。有趣的是，当等摩尔的相反手性的对映体纯分子方块在溶液中混合时，会形成一种具有C(2)对称性的新的内消旋二聚金属环。这一结果表明这些金属环中M - 吡啶键的不稳定性，这可能会阻碍它们在许多对映选择性过程中的应用。