Structural characterization of Langmuir-Blodgett films derived from multisulfur heterocycles

Y. Zhang, M. A. Firestone, T. B. Rauchfuss, P. W. Bohn

Research output: Contribution to journalArticlepeer-review


A novel multisulfur heterocyclic compound with alkyl chains, C3S5(C18H37)2 (4,5-bis(octadecylthio)-1,3-dithiole-2-thione), has been synthesized and fabricated into Langmuir-Blodgett (LB) films. The structure of this film on SiO2 slides has been studied using X-ray photoelectron spectroscopy (XPS) and IR and UV transmission linear dichroism (LD) measurements. From the isotherm, it is known that the Langmuir film at the air-water interface is a bilayer. Angle-resolved XPS of films transferred to SiO2 show that the alkyl chains of the molecule form the topmost layer of the film, with the C3S5 ring underneath the alkyl layer. Electronic structure calculations indicate that the transition moment associated with the observed UV band lies coincident with the C2 axis of the C3S5 ring group. In order to properly interpret the polarized absorption data, a simple model addressing the local field effect in LD measurements was developed. Incorporating measured information on the polarizability of the chromophore, UV and IR LD measurements showed the ring plane and the chains to be stacked at 69° and 20°, respectively, relative to the surface normal. These data coupled with the XPS results permitted a structural model to be constructed which accounts for the multilayer structure of the transferred film.

Original languageEnglish (US)
Pages (from-to)13804-13810
Number of pages7
JournalJournal of physical chemistry
Issue number32
StatePublished - Aug 8 1996

ASJC Scopus subject areas

  • General Engineering
  • Physical and Theoretical Chemistry


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