To develop better polymeric materials for optical-resolution membranes, we synthesized nine chiral phenylacetylenes containing pinanyl groups. We used them to investigate the effects of chemical structures, including the number and position of the chiral groups in the monomers, on the induction of chirality in the main chain during polymerization and on the degree of enantioselectivity in the permeation of the polymeric membranes. The monomers included six new chiral p-(oligomethylpinanylsiloxanyl)phenylacetylenes. The homopolymerizations of these nine monomers with a Rh complex produced high-molecular-weight polymers (molecular weight = 10(5)-10(6)). Of the five polymers with a chiral pinanyl group at the 1-position of each oligosiloxanyl group, all except for two polymers showed high molar ellipticity in the main-chain region in the circular dichroism spectra. This finding indicated that these polymers had a chiral helical main chain. The membranes fabricated from all the polymers synthesized in this study were high-quality, except for two polymers. All these membranes showed enantioselective permeabilities for two amino acids and an alcohol. The membranes from the polymers with a chiral helical backbone, a high content of pinanyl groups, no oligodimethylsiloxane moieties, or a combination of these showed good enantioselectivities ( = 1.7-640) in permeation. We propose that the sense of the main-chain helicity determined the selectivity. (C) 2004 Wiley Periodicals, Inc.