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Aromatic Embrace Motifs for Bulk Supramolecular Polymers
Author(s) -
Lanigan Nicholas,
Assoud Abdeljalil,
Zhang Wei,
Wang Xiaosong
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903138
Subject(s) - supramolecular chemistry , polymer , cyclopentadienyl complex , amorphous solid , crystallization , glass transition , materials science , melting temperature , molecule , polymerization , structural motif , crystallography , crystal structure , polymer chemistry , chemistry , chemical physics , organic chemistry , composite material , catalysis , biochemistry
Abstract Frequently encountered in crystalline materials, aromatic embraces (AEs) are formed when arylated molecules interact through multiple concerted aromatic interactions. AEs are a robust motif that is suitable for the preparation of amorphous bulk supramolecular polymers (BSPs). Crystal engineering revealed that the polymorphic compound (PPh 3 )(Cp)Fe(CO){CO(CH 2 ) 5 CH 3 } (Cp=cyclopentadienyl), known as FpC 6 , assembled into various chain structures through several AE motifs. Upon melting, FpC 6 always adopted the same AE motif, which extended into the corresponding embracing “ladder” chains. The resultant BSP displayed typical polymer behaviour, including the presence of a glass transition and viscoelasticity, which allowed the effect of thermal history on the polymerisation behaviour to be explored. The ladder chains formed by the AE remain assembled at temperatures of up to 130 °C and were able to effectively suppress crystallisation during cooling. The ability of the AE to form chains at high temperatures and suppress crystallisation is a new opportunity to advance the field of BSPs and supramolecular chemistry.