Sponsor
This work was supported by grant no. 324139 of the Research Council of Norway (A.G.) and grant nos. 129270 and 132504 of South African National Research Foundation (J.C.).
Published In
The Journal of Physical Chemistry. A
Document Type
Article
Publication Date
1-30-2025
Abstract
Presented herein is a DFT/TDDFT study of -tetrakis(4-hydroxyphenyl)porphyrin (H[THPP]) and its Meso-deprotonated tetraanionic form; the latter was modeled as both a free tetraanion and with various counterions. Based on our calculations, the experimentally observed hyperporphyrin spectra are attributed to an admixture of phenol/phenoxide character into the a-type HOMO of tetraphenylporphyrin. The admixture results in an elevation of the orbital energy of the HOMO in relation to other frontier orbitals, which accounts for the observed spectral redshifts. The calculations underscore differences in the performance of different exchange-correlation functionals. Thus, while the popular hybrid functional B3LYP greatly exaggerates the redshift of the far-red hyperporphyrin band of -deprotonated H[THPP], the range-separated functional CAMY-B3LYP predicts a more moderate redshift. The latter, however, fails to reproduce experimentally observed absorptions in the 550-600 nm range, potentially underscoring the still imperfect modeling of anionic hyperporphyrins.
Rights
This publication is licensed under CC-BY 4.0 . Copyright © 2025 The Authors. Published by American Chemical Society
Locate the Document
DOI
10.1021/acs.jpca.4c07216
Persistent Identifier
https://archives.pdx.edu/ds/psu/43139
Citation Details
Conradie, J., Wamser, C. C., & Ghosh, A. (2025). Understanding Anionic Hyperporphyrins: TDDFT Calculations on Peripherally Deprotonated meso-Tetrakis(4-hydroxyphenyl)porphyrin. The Journal of Physical Chemistry A, 129(6), 1591–1598.
