Synthesis and spectroscopic study of diphenylamino-substituted phenylene-(poly)ethynylenes: remarkable effect of acetylenic conjugation modes

A series of diphenylamino-substituted phenylene-(poly)ethynylenes were successfully synthesized by a combination of Sonogashira coupling and double elimination protocol of β-substituted sulfones. When UV-light was irradiated, the amino-substituted phenylene-(poly)ethynylene emitted strong luminescence. The emission underwent a large bathochromic shift in polar solvent because of stabilization of their charge-separated excited states. Analyses of fluorescence life times of aminoacetylenes revealed that radiationless process was suppressed in the polar solvent CH2Cl2, resulting in high quantum yields.