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1,3,5‐tricorannulenylbenzene: stereochemistry, reduction and supramolecular dimerization of a branched oligocorannulene
Author(s) -
Eisenberg David,
Quimby Jennifer M.,
Scott Lawrence T.,
Shenhar Roy
Publication year - 2013
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.2951
Subject(s) - chemistry , dimer , supramolecular chemistry , stereochemistry , aryl , stacking , molecule , alkane stereochemistry , crystallography , computational chemistry , alkyl , organic chemistry
Oligocorannulenes are polyarenes composed of several corannulene units that are covalently linked. Their behavior arises both from the diverse properties of each corannulenyl unit and from the interactions between them. In this paper, we present the synthesis, stereochemistry, reduction, and self‐assembly properties of a novel type of oligocorannulene: branched 1,3,5‐tricorannulenylbenzene. Several stereodynamical elements combine to give rich stereochemistry: bowl‐to‐bowl inversion , rotation about the aryl‐aryl single bonds, and residual stereoisomerism of molecular propellers. Reduction with lithium metal yields an intermediate hexaanion and ultimately produces a highly charged dodecaanion. Self‐diffusion NMR demonstrates that the dodecaanion undergoes supramolecular dimerization through charged polyarene stacking, wherein two molecules are linked at all three contact points. The preference for dimerization over dendrimerization is attributed to an entropic effect. The dimer is found to undergo complex structural dynamics, as well as ion‐pairing dynamics, as revealed by variable‐temperature 1 H‐ and 7 Li‐NMR. Copyright © 2012 John Wiley & Sons, Ltd.