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Chiral Interactions in Azobenzene Dimers: A Combined Experimental and Theoretical Study
Author(s) -
Painelli Anna,
Terenziani Francesca,
Angiolini Luigi,
Benelli Tiziana,
Giorgini Loris
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401081
Subject(s) - azobenzene , chemistry , computational chemistry , molecule , organic chemistry
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.