The porphyrin center as a regulator for metal-ligand covalency and pi hybridization in the entire molecule
- The central moiety of porphyrins is shown to control the charge state of the inner complex and links it by covalent interaction to the peripheral substituents. This link, which enables the versatile functions of porphyrins, is not picked up in the established, reduced four orbital picture [Gouterman, J. Mol. Spectrosc., 1961, 6, 138]. X-ray absorption spectroscopy at the N K-edge with density functional theory approaches gives access to the full electronic structure, in particular the pi* manifold beyond the Gouterman orbitals. Systematic variation of the central moiety highlights two linked, governing trends: The ionicity of the porphyrin center increases from the aminic N-H to N-Cu to N-Zn to N-Mg to the iminic N:. At the same time covalency with peripheral substituents increases and compensates the buildup of high charge density at the coordinated nitrogen sites.
Author details: | Robby BüchnerORCiDGND, Mattis FondellORCiD, Robert HaverkampORCiD, Annette PietzschORCiD, Vinícius Vaz da CruzORCiD, Alexander FöhlischORCiDGND |
---|---|
DOI: | https://doi.org/10.1039/d1cp03944j |
ISSN: | 1463-9076 |
ISSN: | 1463-9084 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/34714305 |
Title of parent work (English): | Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies |
Publisher: | Royal Society of Chemistry |
Place of publishing: | Cambridge |
Publication type: | Article |
Language: | English |
Date of first publication: | 2021/10/29 |
Publication year: | 2021 |
Release date: | 2023/11/10 |
Volume: | 23 |
Issue: | 43 |
Number of pages: | 8 |
First page: | 24765 |
Last Page: | 24772 |
Funding institution: | ERC-ADG-2014 - Advanced Investigator Grant under the Horizon 2020 EU [669531 EDAX] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer review: | Referiert |
Publishing method: | Open Access / Hybrid Open-Access |
License (English): | Creative Commons - Namensnennung 3.0 Unported |