Synthesis of Novel Polysiloxanes Containing Charge Transporting and Second-Order Nonlinear Optical Functionalities with Atom Economical Constructs

Abstract

Novel, highly functionalized polysiloxanes were prepared in which each repeat unit bears, on average, one charge transporting and one to two second-order nonlinear optical chromophores. Covalent attachment of charge-transporting carbazole or diphenylamine derivatives was realized through efficient Pt-catalyzed hydrosilylation. Poly(hydrogen methylsiloxane) was reacted with 9-(2-propenyl)carbazole or (N-phenyl-N-2-propenylamino)benzene, affording poly[methyl-3-(9-carbazolyl)propylsiloxane] and poly[methyl-3-(N,N-diphenylamino)propylsiloxane], respectively. Rather remarkable regiospecific bromination of the two arylamine-containing siloxane polymers was achieved using benzyltrimethylammonium chlorobromate, resulting in the formation of poly[methyl-3-(N(3,6-dibromocarbazolyl))propylsiloxane] and poly[methyl-3-(N,N-bis(4-bromophenyl)amino)propylsiloxane]. Pd-catalyzed Heck-type coupling of the arylbromide-bearing polysiloxanes with either vinylbenzenephosphonic acid diethyl ester or 4-nitrostyrene afforded st...