Comprehensive investigation of the triplet state electronic structure of free-base 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin by a combined advanced EPR and theoretical approach

Antonio Barbon; Maria Giulia Dal Farra; Susanna Ciuti; Marco Albertini; Luca Bolzonello; Laura Orian; Marilena Di Valentin

doi:10.1063/1.5131753

Comprehensive investigation of the triplet state electronic structure of free-base 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin by a combined advanced EPR and theoretical approach

J Chem Phys. 2020 Jan 21;152(3):034201. doi: 10.1063/1.5131753.

Authors

Antonio Barbon¹, Maria Giulia Dal Farra¹, Susanna Ciuti¹, Marco Albertini¹, Luca Bolzonello¹, Laura Orian¹, Marilena Di Valentin¹

Affiliation

¹ Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy.

PMID: 31968969
DOI: 10.1063/1.5131753

Abstract

The nature of the photoexcited triplet state of free-base 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H₂TPPS^4-) has been investigated by advanced Electron Paramagnetic Resonance (EPR) techniques combined with quantum chemical calculations. The zero-field splitting (ZFS) parameters, D and E, the orientation of the transition dipole moment in the ZFS tensor frame, and the proton hyperfine couplings have been determined by magnetophotoselection-EPR and pulse electron-nuclear double resonance spectroscopy. Both time-resolved and pulse experiments exploit the electron spin polarization of the photoexcited triplet state. Comparison of the magnetic observables with computational results, including CASSCF calculations of the ZFS interaction tensor, provides an accurate picture of the triplet-state electronic structure. The theoretical investigation has been integrated with a systematic analysis on the parent free-base porphyrin molecule to assess the effect of the sulfonatophenyl substituents on the magnetic tensors. Additionally, the magnetophotoselection effects are discussed in terms of tautomerization in the excited singlet state of H₂TPPS^4-.