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Superphenylphosphines: Nanographene-based Ligands That Control Coordination Geometry and Drive Supramolecular Assembly
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2018-01-09 , DOI: 10.1021/jacs.7b12251
Jordan N. Smith 1 , James M. Hook 2 , Nigel T. Lucas 1
Affiliation  

Tertiary phosphines remain widely utilized in synthesis, most notably as supporting ligands in metal complexes. A series of triarylphosphines bearing one to three hexa-peri-hexabenzocoronene (HBC) substituents has been prepared by an efficient divergent route. These "superphenylphosphines", P{HBC(t-Bu)5}nPh3-n (n = 1-3), form the palladium complexes PdCl2L2 and Pd2Cl4L2 where the isomer distribution in solution is dependent on the number of HBC substituents. The crystalline structures of five complexes all show intramolecular π-stacking between HBC-phosphines to form a supramolecular bidentate-like ligand that distorts the metal coordination geometry. When n = 2 or 3, the additional HBC substituents engage in intermolecular π-stacking to assemble the complexes into continuous ribbons or sheets. The phosphines adopt HBC's characteristics including strong optical absorption, green emission, and redox activity.

中文翻译:

超苯基膦:基于纳米石墨烯的配体,控制配位几何并驱动超分子组装

叔膦仍然广泛用于合成,最显着的是作为金属配合物中的支持配体。通过有效的发散路线制备了一系列带有 1 到 3 个六邻六苯并晕苯 (HBC) 取代基的三芳基膦。这些“超苯基膦”,P{HBC(t-Bu)5}nPh3-n (n = 1-3),形成钯配合物 PdCl2L2 和 Pd2Cl4L2,其中溶液中的异构体分布取决于 HBC 取代基的数量。五种配合物的晶体结构均显示 HBC-膦之间的分子内 π 堆积,形成超分子双齿状配体,扭曲金属配位几何。当 n = 2 或 3 时,额外的 HBC 取代基参与分子间 π 堆积,将复合物组装成连续的带状或片状。膦采用HBC'
更新日期:2018-01-09
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