Incorporation into a redox-active pentasil zeolite [(Na,H)-ZSM-5] converted 2-arylhexa-1,5-dienes (9a-c; aryl = phenyl, tolyl, anisyl) into 1-arylcyclohexane-1,4-diyl radical cations, 10a-c ̇+. The ESR spectra of 10a-c ̇+ (six lines, g = 2.0026; a = 9.0 G) indicated the presence of five essentially equivalent nuclei, indicating limited delocalization of spin and charge into the phenyl group. Sequestered in the pores of ZSM-5, the three species 10a-c ̇+ are stable at room temperature, in striking contrast to the parent radical cation in cryogenic matrices: cyclohexane-1,4-diyl radical cation is converted to cyclohexene radical cation above 90 K. The structures of radical cation 10a ̇+ (X = H) and of the unsubstituted parent were probed by density functional theory (DFT) and ab initio calculations.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry