Electronic properties of oligophenylenevinylene and oligophenyleneethynylene arrays constructed on the upper rim of a calix[4]arene core

Abstract

Heck and Sonogashira cross-coupling reactions have been used for the functionalization of the upper rim of a tetraiodinated calix[4]arene. In this way, oligophenylenevinylene (OPV) and oligophenyleneethynylene (OPE) arrays have been constructed on the calix[4]arene core to produce covalent assemblies of four π-conjugated chromophores. Electrochemical properties have been investigated by cyclic voltammetry in different solvent/electrolyte systems. Both OPV and OPE calixarenes show the simultaneous reduction of three out of four units, followed, at more negative potential, by the reduction of the fourth unit. This behaviour can be rationalized in view of a partial deconjugation in one OPV or OPE unit. On the other hand, these calixarenes show only oxidation processes corresponding to the exchange of one electron, thus demonstrating the lack of electrochemical equivalency of the OPV or OPE units, in contrast to the reduction behaviour. Electronic absorption and emission spectra have been recorded in solvents of different polarity (toluene, dichloromethane, and benzonitrile). The absorption spectra of the OPV calixarene do not match to the sum of the component units as a consequence of the partial deconjugation of the OPV arms in the calixarene structure. On the contrary, fluorescence spectra, quantum yields and excited state lifetimes of the OPV calixarene are nearly identical to those of the corresponding model compound. The trend of the absorption and emission spectra for the OPE calixarene is reversed relative to that of the OPV counterpart. Absorption spectra are well-matched with those of four trimeric OPE fragments but emission spectra exhibit, besides the typical OPE monomeric fluorescence, a broader and longer-lived emission feature on the low-energy spectral side, attributable to excimer-type interactions. Therefore the arrangement of OPV or OPE units within the same calix-4-arene skeleton brings about different effects on the electronic and luminescence properties of the multicomponent system.