Synthesis and Photophysical Properties of Extended π-Conjugative and Push-Pull-Type 1,4-Diaryl-1-thio-1,3-butadienes Incorporated in a Dibenzobarrelene Skeleton

1,4-Bis(p-ethynylphenyl)-1-thio-1,3-butadiene derivatives incorporated in a dibenzobarrelene skeleton were yielded by Sonogashira reactions of the corresponding 1,4-bis(p-halophenyl) derivatives, and push pull-type sulfoxide and sulfone derivatives were obtained by oxidation of the amino derivative prepared by Buchwald-Hartwig reaction of the 1,4-bis(p-halophenyl) derivatives. These compounds show red-shifted yellow and orange fluorescence [lambda(em)(CH2Cl2) = 522-562 nm, lambda(em)(solid) = 522-580 nm] in comparing with the unsubstituted, 1,4-diphenyl-1-thio-1,3-butadiene derivative [lambda(em)(CH2Cl2) = 491 um, lambda(em)(solid) = 483 nm].