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

Year: 2021

Authors: Ghidinelli S., Abbate S., Mazzeo G., Paolesse R., Pomarico G., Longhi G.

Autors Affiliation: Univ Brescia, Dept Mol & Translat Med, I-25123 Brescia, Italy; Natl Inst Opt INO, Res Unit Brescia, CNR, I-25123 Brescia, Italy; Univ Roma Tor Vergata, Dept Chem Sci & Technol, I-00133 Rome, Italy; Res Ctr Colloids & Nanosci, CSGI, I-50019 Florence, 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).

Journal/Review: ACS OMEGA

Volume: 6 (40)      Pages from: 26659  to: 26671

More Information: This study was carried out with the support of resources of Big&Open Data Innovation Laboratory (BODaI-Lab), University of Brescia, granted by Fondazione Cariplo and Regione Lombardia and of Computing Center CINECA (Bologna), Italy. Funding from the Italian Ministry of Education, University and Research (MIUR) through the PRIN 2017 program (Project 2017A4XRCA_003 Physico-chemical Heuristic Approaches: Nanoscale Theory of Molecular Spectroscopy [PHANTOMS]) and University of Brescia Research Fund (ex 60%) is acknowledged. We thank PhD School: Molecular Genetics, Biotechnologies and Experimental Medicine, University of Brescia for covering publication costs.
KeyWords: Magnetic Circular-dichroism; Pi-electron Systems; Polarized Luminescence; B-terms; Europium(iii) Complexes; Molecular-structures; Algebraic-solution; Optical-activity; A-terms; Corrole
DOI: 10.1021/acsomega.1c04028

Citations: 13
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