Structure and electronic communication amongst oligophenylenevinylenes: Intramolecular conjugation of higher dimensionality

A wide range of distyrylbenzene derivatives and [2.2]paracyclophane-based analogs were studied in terms of spectroscopic properties and solid state structure. A series of distyrylbenzene derivatives were examined to find trends in the evolution of structural order. Changes in the positional relationship between chromophores in the solid state could be effectively manipulated in binary solid phases. Through the incorporation of [2.2]paracyclophane into the backbone of small oligophenylenevinylenes, charge transfer type molecules were created that allow for the transmission of electron density through-space upon excitation. By building chromophores around the paracyclophane core, the point and extent of interchromophore contact is well-defined and the identity of molecules paired in such a way can be controlled with the correct regiochemistry. The role of through-space intermolecular charge transfer is examined in the context of nonlinear optical phenomena. Extension of conjugation from one dimension to higher dimensionality leads to unusual spectroscopic and NLO behavior. The synthesis, UV-Vis absorption and emission as well as NLO analysis is discussed. Also, solid state characterizations of the paracyclophane models are examined in terms of their monomer components.