Spectral properties and photophysical processes of meso styryl substituent triphenylamine-porphyrin derivatives

This work reports the synthesis and spectral properties of meso-styryl substituted triphenylamine-porphyrin derivatives, mP-BLP, mPPC-BLP and their metal coordinated complexes. The photophysical processes were analyzed and related to the meso-groups and centre metal ions. The meso styryl substituent in mP-BLP and its complexes are able to extend the conjugation of porphyrin macrocycle to the styryl motif, increase light harvesting ability and accelerate intersystem crossing (ISC) process. A large dihedral angle between the meso-styryl group and porphyrin macrocycle would prohibit the delocalization of electrons between the two motifs and induce the occurrence of solvation decay process. Increasing the electron-withdrawing ability of meso-substituent via additional pyrimidine group could promote the photoinduced intramolecular electron transfer (PIET) process for mPPC-BLP. Moreover, the coordination of metal ions would significantly accelerate the photophysical processes of both mP-BLP and mPPC-BLP. Specially, the Mg2+ is helpful to the ISC process whereas Zn2+ is adverse to the ISC process, while Cu-2(+) would boost the non-radiation process. Furthermore, Zn2+ is able to promote the PIET process of mPPC-BLP, exhibiting the highest charge-separated tendency among these porphyrins. mPPC-ZnBLP-based dye-sensitized solar cell (DSSC) devices show the highest power conversion efficiency (PCE). The photovoltaic performance of DSSC devices reveals the significancy of the photoinduced charge-separated tendency for the design of porphyrin sensitizers.