Polyacetylene-type networks prepared by coordination polymerization of diethynylarenes: New type of microporous organic polymers

摘要

Microporous organic polymers (MOP) of a new type have been synthesised in high yields by a simple coordination polymerization of 1,3-diethynylbenzene, 1,4-diethynylbenzene and 4,4′-diethynylbiphenyl catalysed by Rh(cod)acac and Rh(nbd)acac complexes. The new MOPs are non-swellable polyacetylene-type conjugated networks consisting of ethynylaryl-substituted polyene main chains that are crosslinked by arylene linkers. Prepared MOP samples have a mole fraction of branching units (by ~(13)C CP/MAS NMR) from 0.30 to 0.47 and exhibit the BET (Brunaer-Emmett-Teller) surface up to 809 m~2 g~(-1) and hydrogen uptake up to 0.69 wt (77 K, H_2 pressure 750 torr). Coordination polymerization of diethynylarenes is revealed to provide high yields of non-swellable polyacetylene-type networks as a new type of microporous organic polymers (MOPs) active in gas adsorption. Networks prepared represent an alternative to poly(aryleneethynylene)-type MOPs. Polymers derived from diethynylbenzenes can be considered as unsaturated analogues of poly(divinylbenzene) networks.