Synthesis,characterization, and photolysis of poly[3,5-di-tert-butyl-4-[(2,4,6-tri-tert-butylphenyl)oxalato]phenylacetylene], a photochemical polyradical precursor

A photochemical precursor to a pendant conjugated polyradical has been synthesized, poly3,5-di-tert-butyl-4-(2,4,6-tri-tert-butylphenyl)oxalato]phenylacetylene], 3 . Irradiation of 3 at 77 K in the solid state at < 300 nm yielded poly(3–5-di-tert-butyl-2-oxyphenyl acetylene), 2 , with 30–40% of the expected number of radical spins. Spin yields on the surface of solid samples appears to be considerably higher. Electron spin resonance experiments showed no evidence of cooperative exchange interaction between the pendant spins. Computational modeling indicated that a major reason for the failure of this and other polyphenylacetylenes to show ferromagnetic exchange between spins is the substantial twisting of the polyacetylene backbone required by steric interactions, leading to deconjugation and a loss of exchange interaction between pendant radicals along the chain. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2167–2176, 1997