title: Chiral interactions in azobenzene dimers: a combined experimental and theoretical study.
abstract: To investigate interchromophore interactions in azobenzene polymers, we have undertaken a thorough spectroscopic analysis of the azodye [(S)-3-pivaloyloxy-1-(4'-nitro-4-azobenzene)pyrrolidine] by modeling the repeating unit of poly[(S)-3-methacryloyloxy-1-(4'-nitro-4-azobenzene)pyrrolidine) and its dimeric derivative whose synthesis is presented here. The analysis of the electronic and Raman spectra of the azodye in several solvents is based on a previously proposed model for polar chromophores in solution. Electronic and CD spectra of the dimeric unit are collected and analyzed within the framework of a new model. On the basis of the information collected from the spectroscopic analysis of the solvated dye, this model accounts for interchromophore interactions in the dimer. The large CD signal measured for the dimer (amounting to about a third of the signal measured for the polymer) suggests the presence of important chiral interactions in the dimeric unit, and is modeled in terms of a right-handed relative orientation of the two chromophores.
authors.affiliation: Dipartimento di Chimica GIAF and INSTM UdR-Parma, Università di Parma viale delle Scienze 17/a, 43100 Parma, Italy. anna.painelli@unipr.it
authors.forename: Anna
authors.initials: A
authors.lastname: Painelli
authors.forename: Francesca
authors.initials: F
authors.lastname: Terenziani
authors.forename: Luigi
authors.initials: L
authors.lastname: Angiolini
authors.forename: Tiziana
authors.initials: T
authors.lastname: Benelli
authors.forename: Loris
authors.initials: L
authors.lastname: Giorgini