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Stereoselective Self-Assembly of Complex Chiral Radial [5]Catenanes Using Half-Sandwich Rhodium/Iridium Building Blocks

Zheng Cui, Xiang Gao, Yue‐Jian Lin, Guo‐Xin Jin

2022Journal of the American Chemical Society48 citationsDOI

Abstract

Herein, we have successfully achieved the stereoselective synthesis of two chiral radial [5]catenanes in a single step through the self-assembly of bidentate ligands containing l-alanine residues and binuclear half-sandwich organometallic rhodium(III)/iridium(III) clips. Remarkably, these two chiral radial [5]catenanes exhibit complex stereochemical structures as revealed by single-crystal X-ray diffraction. The eight binuclear units and eight bidentate ligands in their solid-state structures all exhibit a single planar chirality, and the interlocking between molecular macrocycles exhibits a single co-conformational mechanical helical chirality. This indicates that the introduction of the point chirality in the ligands enables the efficient stereoselective construction of mechanically interlocked molecules. Furthermore, by using ligands containing d-alanine residues, radial [5]catenanes with the opposite planar chirality and opposite co-conformational mechanical helical chirality have also been obtained.

Topics & Concepts

CatenaneChirality (physics)ChemistryPlanar chiralityRhodiumDenticityIridiumCrystallographyStereoselectivityStereochemistryAxial chiralityMoleculeEnantioselective synthesisCrystal structureCatalysisOrganic chemistryPhysicsQuantum mechanicsQuarkChiral symmetry breakingNambu–Jona-Lasinio modelSupramolecular Chemistry and ComplexesCrystallography and molecular interactionsSupramolecular Self-Assembly in Materials
Stereoselective Self-Assembly of Complex Chiral Radial [5]Catenanes Using Half-Sandwich Rhodium/Iridium Building Blocks | Litcius