Novel side-chain liquid-crystalline copolymers (SCLCPs) were synthesized via the Pd(II) catalyzed alternating copolymerization of mesogenic 1-alkenes and carbon monoxide. For methoxybiphenyl mesogens, these copolymers exhibited highly ordered smectic E mesophases and high glass transition temperatures. The transition temperatures of these polymers were tuned by altering the spacer length or by dilution of mesogen-containing alkenes with 1-hexene. Polymers with cyanobiphenyl or methoxyazobenzene mesogens exhibited nematic mesophases. These polymers were the first ever nitrogen containing copolymers of this type. Increase of the spacer length or the 1-hexene content of methoxybiphenyl-containing copolymers resulted in a decrease of the surface polarity of spincoated films. The decomposition temperature of these SCLCPs started far above the isotropization temperature of the polymers.
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