J. Phys. Chem. C 2008, 112, 8099–8104
8099
High-Temperature Chromophores and Perfluorocyclobutyl Copolymers for Electro-optic Applications† Stephen M. Budy, S. Suresh,‡ Bryan K. Spraul,§ and Dennis W. Smith, Jr.* Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson UniVersity, Clemson, South Carolina 29634 ReceiVed: February 4, 2008; ReVised Manuscript ReceiVed: March 19, 2008
The synthesis and hyperpolarizabilities of a series of push-pull chromophores containing a bis-(4methoxyphenyl) amine donor and efficient acceptor bridges with thiophene and ring-locked polyene are presented. The chromophores are readily soluble in common organic solvents and exhibit high thermal decomposition temperatures (highest Td was 358 °C). Molecular hyperpolarizabilities (β) of the chromophores were measured by hyper-Raleigh scattering at 1604 nm (highest β was 20 000 × 10-30 esu). The electrochemical behavior of the chromophores was studied by cyclic voltammetry and agreed well with the observed intrinsic nonlinearities. In addition, preliminary results of conjugated polyene chromophores containing aryl trifluorovinyl ether monomers were synthesized and copolymerized via thermal cyclodimerization, affording perfluorocyclobutyl aryl ether polymers with high glass transitions (highest Tg was 224 °C) and a good thermal stability (typical Td was >350 °C). These chromophores can be used to develop electro-optic materials due to their large optical nonlinearities, good absorption characteristics, high thermal stability, and excellent solubility with organic solvents and polymeric materials. Introduction Electro-optic (EO) materials are of great interest due to their potential applications in optical data transmission and optical information processing.1–3 Organic polymers containing push-pull chromophores are important for the realization of high-speed EO devices with very broad bandwidths (200 GHz), which can be operated at low voltages (
