Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin

Robby Büchner; Vinícius Vaz da Cruz; Nitika Grover; Asterios Charisiadis; Mattis Fondell; Robert Haverkamp; Mathias O. Senge; Alexander Föhlisch

doi:10.1039/D1CP05420A

Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin†

Robby Büchner,

*^ab Vinícius Vaz da Cruz,

*^b Nitika Grover,

^c Asterios Charisiadis,^c Mattis Fondell,

^b Robert Haverkamp,^ab Mathias O. Senge

*^d and Alexander Föhlisch

^ab

Author affiliations

* Corresponding authors

^a Institute of Physics and Astronomy, University of Potsdam, Karl-Liebknecht-Str. 24-25, 14476 Potsdam, Germany
E-mail: rbuechner@uni-potsdam.de

^b Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Str. 15, Berlin, Germany
E-mail: vinicius.vaz_da_cruz@helmholtz-berlin.de

^c School of Chemistry, Chair of Organic Chemistry, Trinity College Dublin, The University of Dublin, Trinity Biomedical Sciences Institute, 152-160 Pearse Street, Dublin 2, Ireland

^d Institute for Advanced Study, Technical University of Munich, Lichtenbergstrasse 2a, 85748 Munchen Garching, Germany
E-mail: mathias.senge@tum.de

Abstract

Free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin stands for the class of powerful porphyrin photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump – N K-edge probe X-ray absorption spectroscopy in combination with time-dependent density functional theory (TD-DFT) gives direct access to the crucial excited molecular states within the unusual relaxation pathway. The efficient intersystem crossing, that is El-Sayed forbidden and not facilitated by a heavy atom is confirmed to be the result of the long singlet excited state lifetime (Q_x 4.9 ns) and thermal effects. Overall, the interplay of stabilization by conservation of angular momenta and vibronic relaxation drive the de-excitation in these chromophores.

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Article information

DOI: https://doi.org/10.1039/D1CP05420A
Article type: Paper
Submitted: 26 Nov 2021
Accepted: 19 Jan 2022
First published: 15 Mar 2022
This article is Open Access

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Phys. Chem. Chem. Phys., 2022,24, 7505-7511

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Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin

R. Büchner, V. Vaz da Cruz, N. Grover, A. Charisiadis, M. Fondell, R. Haverkamp, M. O. Senge and A. Föhlisch, Phys. Chem. Chem. Phys., 2022, 24, 7505 DOI: 10.1039/D1CP05420A

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Physical Chemistry Chemical Physics

Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin†

Abstract

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Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin

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