Affiliation:
1. Sorbonne Université, CNRS Institut Parisien de Chimie Moléculaire Equipe Chimie des Polymères 4 Place Jussieu 75005 Paris France
Abstract
AbstractAggregation of supramolecular helices, for example through interdigitation of their alkyl side chains or through more directional supramolecular interactions, leads to hierarchical architectures with original structural and chiroptical properties. However, when a chiral monomer (the “sergeant”) is introduced as a minor component in these assemblies composed of a majority of achiral monomers (the “soldiers”), it is not clear how the aggregation changes the ability of the sergeant to induce a preferential helicity to the polymer main chain (the so‐called “sergeants‐and‐soldiers” effect). This study reports a detailed investigation of the influence of [Cu(OAc)2⋅H2O] coordination on the structure and chiroptical properties of helical hydrogen‐bonded co‐assemblies composed of a catalytically‐active benzene‐1,3,5‐tricarboxamide (BTA) monomer, acting as the “soldier”, and an enantiopure BTA monomer derived from cyclohexylalanine, playing the role of the “sergeant”. The copper actually significantly influences the extent of the “sergeants‐and‐soldiers” effect since it acts as a crosslink that induces some chiral defects in the supramolecular helices. These crosslinks appear to be preserved during the catalytic hydrosilylation of 4‐nitroacetophenone. The aggregation of helices through the formation of copper crosslinks is reversible since homochiral single helices are exclusively formed in the case of sergeant‐rich assemblies. The fact that both main chain and side chain aggregation affects the chiroptical properties of supramolecular helices must be considered in the design of elaborated chiral materials.
Funder
Agence Nationale de la Recherche
Instituto Nacional de Ciência e Tecnologia em Nanomateriais de Carbono
China Scholarship Council
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
2 articles.
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