Abstract
The photoisomerization characteristic parameters [photostationary states (PSSs), cross section σ, and quantum yield η] of indolyl fulgimide compounds dispersed in solution are quantitatively compared to those of the same compounds covalently immobilized as a monolayer on functionalized Si(111) surfaces (see Adv. Mater. 2013, 25, 416). The photoisomerization kinetics of fulgimide compounds in solution is monitored using UV–vis spectroscopy and that of monolayers is monitored by in situ calibrated Fourier transform infrared spectroscopy. Although the isomeric composition at PSSs is very similar in solution and at surfaces, a strong influence of the incident light polarization is found on photoisomerization cross section σ (σs ≪ σp < σsol). Accounting for the local excitation electromagnetic field indicates that the fulgimide groups adopt a preferential tilt angle with respect to the surface normal and their transition dipole is almost parallel to the surface plane for either C or E/Z isomers. Density functi...
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