Dendrimers Made of Porphyrin Cores and Carbazole Chromophores as Peripheral Units. Absorption Spectra, Luminescence Properties, and Oxidation Behavior

Abstract

Luminescent and redox-active porphyrin-based dendrimers of first and second generation have been synthesized, and their absorption spectra, photophysical properties, and oxidation behavior have been investigated, together with those of the corresponding aldehyde carbazole precursors. All the dendrimers contain a porphyrin core and carbazole-based chromophores as branches. The structural formulas of the new species are represented in Figures 1 and 2, with the corresponding schematizations. The absorption spectra of the aldehyde carbazole precursors A1-A6 in dichloromethane exhibit intense transitions in the UV region, centered on the carbazole and benzaldehyde subunits. The lowest-energy absorption bands receive contribution from charge-transfer transitions. Compounds A1-A6 are luminescent at room temperature in fluid solution; such a luminescence is attributed to twisted intramolecular charge-transfer excited states. The luminescence at 77 K in a rigid matrix is blue-shifted with respect to room-temperature emission and is assigned to locally excited states. Absorption spectra of the porphyrin-cored dendrimers P1-P6 appear additive as they are constituted by visible bands due to porphyrin absorption and bands in the UV region due to transitions centered on the carbazole-based branches. Emission spectra of P1-P6 both at 77 K and at room temperature are typical of porphyrin species and independent of excitation wavelength, indicating that the light collected by the peripheral chromophores is quantitatively transferred to the core. All the compounds exhibit a rich oxidation behavior in 1,2-dichloroethane solution, with reversible processes centered on the different carbazole subunits. Interaction between the different carbazole centers depends on the size of the spacer interposed.