The cyclopolymerization of polar, ionic N,N-dibutyl-N,N-dipropargylammonium bis(trifluoromethylsulfonyl)imide (M1), N,N-dimethyl-N,N-dipropargylammonium bis(trifluoromethylsulfonyl)imide (M2), N,N-dipropargylmorpholinium bis(trifluoromethylsulfonyl)imide (M3), and N-propyl-N,N-dipropargylamine (M4) using
five different well-defined Schrock- and trifluoroacetate-modified Grubbs-type initiators was investigated. Ru-based initiators allowed for the polymerization of M1−M3 with average isolated polymer yields around 25−40%, however, poly-M2 and poly-M3 thus prepared consisted >95% of five-membered ring structures, i.e.,
(3,4-(1H-2,5-dihydropyrrolylene)vinylene)s units. In contrast, the use of the Schrock type initiator Mo(N-2,6-iPr2C6H3)(CHMe2Ph)(OC(CH3)(CF3)2)2 allowed for quantitative polymer yields, whereas, poly-M2 prepared by
the action of this initiator was based on both five- and six-membered, i.e., (3,5-(1,2,5,6-tetrahydropyridinylene)methylidene) cyclic units. Polymers were synthesized with molecular weights M
n < 21 800 g/mol and polydispersity
indices in the range of 1.04 < PDI < 1.37 and 1.01 < PDI < 1.08 with Ru- and Mo-based initiators, respectively.
They were additionally investigated for their thermal stability and ionic conductivity. Finally, the solvatochromic
behavior of the polymers prepared was studied. Particularly, solutions of poly-M1 prepared by the action of
Ru-based initiators displayed a high sensitivity toward traces of water in N,N-dimethylformamide.