Theoretical and experimental analysis of porphyrin derivatives with suitable anchoring groups for DSSC applications

Abstract

In this contribution, different porphyrin derivatives were experimentally synthesized and theoretically analyzed using several electronic structure methods to study the geometrical and electronic properties of A4, trans-A2B[Formula: see text]and A3B porphyrins bearing several functional groups (–OH, –COOH, -3,5-di-[Formula: see text]Bu, –OCH2CH2CH2COOEt and –OMe) suitable to be employed as dyes in Dye Sensitized Solar Cells (DSSC). A4 (R [Formula: see text] -H, -OMe, -OH, -3,5-di-tert-butyl, –OCH2CH2CH2COOEt) and A3B (R[Formula: see text][Formula: see text]R[Formula: see text][Formula: see text]R[Formula: see text][Formula: see text]–H; R[Formula: see text][Formula: see text]–OH and R[Formula: see text][Formula: see text]-3,5-di-[Formula: see text]Bu) porphyrins were synthesized and characterized by UV-vis and 1H NMR spectroscopies for comparison. The geometrical parameters were analyzed in the ground state and gas phase using the semiempirical method PM6 and the DFT functionals M06-2X and B3LYP, in combination with the 6-31G(d), DZVP and TZVP basis set. For calculations of the electronic and excited state properties, CAM-B3LYP, M06-2X and HSE06, using SMD as solvation model, were applied. This study revealed that HSE06/DZVP protocol is the best methodology to simulate electronic spectra in these porphyrin derivatives. Indeed, whereas substituent groups did not significantly affect the geometrical structure of the porphyrin derivatives studied, they do influence their electronic structures, mainly in the LUMO (lowest unoccupied molecular orbital) energy levels.