Polyacetylene-Type Networks Prepared by Coordination Polymerization of Diethynylarenes: New Type of Microporous Organic Polymers

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 13C CP/MAS NMR) from 0.30 to 0.47 and exhibit the BET (Brunaer-Emmett-Teller) surface up to 809 m2 g-1 and hydrogen uptake up to 0.69 wt% (77 K, H2 pressure 750 torr).