Fourier transform infrared and Raman spectra of a novel series of neutral alpha,omega-bis(mesitylthio)oligothiophenes and some alpha,omega-bis(mesitylthio)oligothiophenes containing ethylenedioxy groups at the beta positions, with various chain lengths have been investigated. Because these compounds contain carbon-sulfur linkages they can be viewed as models for prototypical surface-bound molecular wires in which the oligomer is linked to the surface by a thiol-metal bond. Thus, interactions between the conjugated moiety and the metallic surface or cluster can be simulated. These studies are very important in order to apply molecular systems in micro and optoelectronic devices. The statements of effective conjugation coordinate theory and density functional theory calculations let us describe the specific electronic interactions between the mesitylthio groups and the oligothiophene backbone. An increased pi-electron delocalization or conjugation length with respect to the alpha,omega-bis(alkyl)oligothiophenes of the same length has been noticed. The inclusion of C=S bridges between the end groups and the central pi-conjugated backbone increases the pi-electron delocalization within the oligomeric chain and precludes the oligothiophene moiety from conjugative interactions with the mesityl rings. (C) 2003 American Institute of Physics.