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Investigation of thermochromism in a series of side-chain, liquid-crystalline, azobenzene-containing polymers

2004; NRC Research Press; Volume: 82; Issue: 1 Linguagem: Inglês

10.1139/v03-170

1480-3291

Stephan Freiberg, François Lagugné‐Labarthet, P. Rochon, Almeria Natansohn,

Surfactants and Colloidal Systems

The thermochromic properties of a series of liquid crystalline polymethacrylates, containing azobenzene side-chains with variable spacer lengths, were investigated. Annealing the amorphous polymer thin films above the glass transition temperature results in a rearrangement of the azobenzene moieties, causing a hypsochromic shift in the electronic absorption spectra. A detailed investigation of the spectral shift was performed by in situ UV–vis spectroscopy and indicated the formation of H-type aggregates by the side-chain chromophores above the glass transition temperature. The rate at which the hypsochromic shift occurs is faster for polymers with shorter spacers since their high glass transition temperature results in a higher thermal energy during the thermochromic effect. Experimentally determined activation energies show that the aggregation occurs primarily due to side-chain relaxation (β-relaxation) and main-chain relaxation (α-relaxation). Further annealing above the isotropization temperature resulted in the onset of deaggregation and in most cases showed that the chromophores were freed from the ordered state.Key words: liquid-crystalline polymer, thermochromic properties, chain relaxation, aggregation, thin films, azobenzene mesogens.