Chirogenesis in Zinc Porphyrins: Theoretical Evaluation of Electronic Transitions, Controlling Structural Factors and Axial Ligation.

circular dichroism density functional calculations porphyrins supramolecular chemistry transition metals

Journal

Chemphyschem : a European journal of chemical physics and physical chemistry
ISSN: 1439-7641
Titre abrégé: Chemphyschem
Pays: Germany
ID NLM: 100954211

Informations de publication

Date de publication:
03 09 2021
Historique:
revised: 24 06 2021
received: 04 05 2021
pubmed: 3 7 2021
medline: 3 7 2021
entrez: 2 7 2021
Statut: ppublish

Résumé

In the present work, sixteen different zinc porphyrins (possessing different meso substituents) with and without a chiral guest were modelled using DFT and TD-DFT approaches in order to understand the influence of various controlling factors on electronic circular dichroism (ECD) spectra. Two major aspects are influenced by these factors: excitation energy of the electronic transitions and their intensity. In the case of excitation energy, the influence increases in the following order: orientation of the peripheral substituents<substituent's nature<axial ligation. However, the deformation of the porphyrin plane does not affect the excitation energies. In the case of intensity, the influence increases as follows: substituent's nature<conrotatory orientation of the peripheral substituents<deformation of the porphyrin plane<disrotatory orientation of the peripheral substituents<axial ligation.

Identifiants

pubmed: 34213815
doi: 10.1002/cphc.202100345
pmc: PMC8457158
doi:

Types de publication

Journal Article Research Support, Non-U.S. Gov't

Langues

eng

Sous-ensembles de citation

IM

Pagination

1817-1833

Subventions

Organisme : Estonian Research Council
ID : PUTJD749
Organisme : Estonian Research Council
ID : PRG399
Organisme : European Union's H2020-FETOPEN
ID : 828779

Informations de copyright

© 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH.

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Auteurs

Irina Osadchuk (I)

Department of Chemistry and Biotechnology, School of Science, Tallinn University of Technology Address, Akadeemia tee 15, 12618, Tallinn, Estonia.
ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France.

Riina Aav (R)

Department of Chemistry and Biotechnology, School of Science, Tallinn University of Technology Address, Akadeemia tee 15, 12618, Tallinn, Estonia.

Victor Borovkov (V)

Department of Chemistry and Biotechnology, School of Science, Tallinn University of Technology Address, Akadeemia tee 15, 12618, Tallinn, Estonia.

Eric Clot (E)

ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France.

Classifications MeSH