title: Photochemical and electronic properties of conjugated bis(azo) compounds: an experimental and computational study.
abstract: We have investigated the photophysical, photochemical and electrochemical properties of two bis(azo) derivatives, (E,E)-m-1 and (E,E)-p-1. The two compounds, which can be viewed as being composed of a pair of azobenzene units sharing one of their phenyl rings, differ only for the relative position of the two azo groups on the central phenyl ring-meta and para for m-1 and p-1, respectively. The UV-visible absorption spectra and photoisomerisation properties are noticeably different for the two structural isomers; (E,E)-m-1 behaves similarly to (E)-azobenzene, while (E,E)-p-1 exhibits a substantial red shift in the absorption bands and a decreased photoreactivity. The three geometric isomers of m-1, namely the E,E, E,Z and Z,Z isomers, cannot be resolved in a mixture by absorption spectroscopy, while the presence of three distinct species can be revealed by analysis of the absorption changes observed upon photoisomerisation of (E,E)-p-1. Quantum chemical ZINDO/1 calculations of vertical excitation energies nicely reproduce the observed absorption changes and support the idea that, while the absorption spectra of the geometrical isomers of m-1 are approximately given by the sum of the spectra of the constituting azobenzene units in their relevant isomeric form, this is not the case for p-1. From a detailed study on the E-->Z photoisomerisation reaction it was observed that the photoreactivity of an azo unit in m-1 is influenced by the isomeric state of the other one. Such observations indicate a different degree of electronic coupling and communication between the two azo units in m-1 and p-1, as confirmed by electrochemical experiments and quantum chemical calculations. The decreased photoisomerisation efficiency of (E,E)-p-1 compared to (E,E)-m-1 is rationalised by modelling the geometry relaxation of the lowest pi-pi* state. These results are expected to be important for the design of novel oligomers and polymers, based on the azobenzene unit, with predetermined photoreactivity.
authors.affiliation: Dipartimento di Chimica G. Ciamician, Università di Bologna, via Selmi 2, 40126 Bologna, Italy.
authors.forename: Federico
authors.initials: F
authors.lastname: Cisnetti
authors.forename: Roberto
authors.initials: R
authors.lastname: Ballardini
authors.forename: Alberto
authors.initials: A
authors.lastname: Credi
authors.forename: Maria Teresa
authors.initials: MT
authors.lastname: Gandolfi
authors.forename: Stefano
authors.initials: S
authors.lastname: Masiero
authors.forename: Fabrizia
authors.initials: F
authors.lastname: Negri
authors.forename: Silvia
authors.initials: S
authors.lastname: Pieraccini
authors.forename: Gian Piero
authors.initials: GP
authors.lastname: Spada