MCD and MCPL Characterization of Luminescent Si(IV) and P(V) Tritolylcorroles: The Role of Coordination Number

Simone Ghidinelli; Sergio Abbate; Giuseppe Mazzeo; Roberto Paolesse; Giuseppe Pomarico; Giovanna Longhi

doi:10.1021/acsomega.1c04028

MCD and MCPL Characterization of Luminescent Si(IV) and P(V) Tritolylcorroles: The Role of Coordination Number

ACS Omega. 2021 Sep 29;6(40):26659-26671. doi: 10.1021/acsomega.1c04028. eCollection 2021 Oct 12.

Authors

Simone Ghidinelli¹, Sergio Abbate^{1

2}, Giuseppe Mazzeo¹, Roberto Paolesse³, Giuseppe Pomarico^{1

4}, Giovanna Longhi^{1

2}

Affiliations

¹ Department of Molecular and Translational Medicine, University of Brescia, Viale Europa 11, 25123 Brescia, Italy.
² National Institute of Optics (INO), CNR, Research Unit of Brescia, c/o CSMT, via Branze 45, 25123 Brescia, Italy.
³ Department of Chemical Science and Technologies, University of Rome Tor Vergata, Via della Ricerca Scientifica snc, 00133 Rome, Italy.
⁴ CSGI, Research Center for Colloids and Nanoscience, Via della Lastruccia 3, Sesto Fiorentino, 50019 Firenze, Italy.

Abstract

Two triarylcorrole complexes, (hydroxy)[5,10,15-tritolylcorrolato]silicon-(TTC)Si(OH) and (dihydroxy)[5,10,15-tritolylcorrolato]phosphorous-(TTC)P(OH) ₂ , have been investigated by magnetic circular dichroism (MCD) and magnetic circularly polarized luminescence (MCPL). The spectroscopic investigations have been combined with explicit calculation of MCD response through time-dependent density functional theory (TD-DFT) formalism. This has allowed us to better define the role of molecular orbitals in the transitions associated with the Soret and Q bands. Besides and more importantly, MCD has made it possible to follow the titration process of (TTC)Si(OH) in dimethyl sulfoxide (DMSO) solution with NaF and of (TTC)P(OH) ₂ in dichloromethane solution with alcohols in a complementary and, we dare say, more sensitive way with respect to absorption and fluorescence data. Finally, the MCPL spectra and the ancillary TD-DFT calculations have allowed us to characterize the excited state of (TTC)Si(OH).