Fourier transform Raman and DFT study of three annulated oligothiophenes with different molecular shapes.

Herein, we study the conjugation properties of three different thienoacenes, each of which has three or four fused thiophene rings, by means of Fourier transform Raman spectroscopy. The B3LYP/6-31G** vibrational analysis of all of the collected spectroscopic data evidences that the selective enhancement of a limited number of Raman scatterings is related to the occurrence in the three thienoacenes of a vibronic coupling between the lowest unoccupied frontier molecular orbital (LUMO) and some Raman-active skeletal nu(C==C) stretching modes of 1600-1300 cm(-1).

Push-pull bithienyl chromophore with an unusual transverse path of conjugation.

The synthesis, structure, and electronic properties of a novel cross-conjugated 10H-bisthienodithiocin-10-dicyanoethylene are reported. The X-ray single-crystal structure of the compound reveals a nonplanar conformation. The FT-IR and FT-Raman spectra of the compound show a great resemblance, which is a spectroscopic observation common to many push-pull systems.

A new route to annulated oligothiophenes.

[reaction: see text] A new convenient method for the construction of thiophene-annulated thieno[2,3-b]thiophenes has been proposed. The key step of the method is ring closure of 10H-bisthienodithiocin-10-one by strong bases. The syntheses of two previously unknown annulated oligothiophenes, thieno[2,3-b]thieno[3',2':4,5]thieno[3,2-d]thiophene (1a) and thieno[3,2-b]thieno[2',3':4,5]thieno[3,2-d]thiophene (1b), have been described to illustrate the success of the method.