Design of Metal-Organic Assemblies via Shape Complementarity and Conformational Constraints in Dual Curvature Ligands  

作　　者：Cui-Lian Liu Eduard O.Bobylev Sébastien Dauriac Brice Kauffmann Koen Robeyns Yann Garcia Joost N.H.Reek Michael L.Singleton 

机构地区：[1]Institute of Condensed Matter and Nanosciences,Universitécatholique de Louvain,Louvain-la-Neuve 1348 [2]Van’t Hoff Institute for Molecular Sciences,University of Amsterdam,Amsterdam 1098 XH [3]Universitéde Bordeaux CNRS,INSERM,UMS3033,Institut Européen de Chimie et Biologie(IECB),33600 Pessac

出　　处：《CCS Chemistry》2023年第11期2506-2518,共13页中国化学会会刊（英文）

基　　金：supported in part through the Concerted Research Action(ARC16/21-074)and the China Scholarship Council(pre-doctoral fellowships for C.-L.L.).

摘　　要：While common in biological systems,building blocks with low symmetry and flexibility pose numerous problems for synthetic self-assembly,such as the formation of isomers of assemblies that are difficult to distinguish and purify.In this work,three aromatic amide-based ligands(L1–L3)with a central 1,8-diazatriptycene core were designed and used for selfassembly with Pd^(2+).While hundreds of stereoisomers based on the conformational flexibility around the amides and the unsymmetrical nonplanar structure of the core are possible upon coordination with the metal,the constraints designed into the ligands direct the self-assembly toward only a single Pd_(2)L_(4)cage(L1)or Pd_(4)L_(8)double-walled metallomacrocycle(L2)structure,even in mixtures of the ligands.This structural approach and the modularity of the ligand synthesis affords ready access to deep cavitands with endohedral functionalization(L3).These results highlight the potential of this new design strategy and open the door to selectively functionalized cavity-based architectures for numerous applications.

关 键 词：metal-organic cageopis isomer selectivity low-symmetry ligands SELF-SORTING self-assembly 

分 类 号：O62[理学—有机化学]