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Dimeric Corrole Analogs of Chlorophyll Special Pairs

Sharma, Vinay K. and Mahammed, Atif and Mizrahi, Amir and Morales, Maryann and Fridman, Natalia and Gray, Harry B. and Gross, Zeev (2021) Dimeric Corrole Analogs of Chlorophyll Special Pairs. Journal of the American Chemical Society, 143 (25). pp. 9450-9460. ISSN 0002-7863. PMCID PMC8249354. https://resolver.caltech.edu/CaltechAUTHORS:20210524-163212708

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Abstract

Chlorophyll special pairs in photosynthetic reaction centers function as both exciton acceptors and primary electron donors. Although the macrocyclic natural pigments contain Mg(II), the central metal in most synthetic analogs is Zn(II). Here we report that insertion of either Al(III) or Ga(III) into an imidazole-substituted corrole affords an exceptionally robust photoactive dimer. Notably, attractive electronic interactions between dimer subunits are relatively strong, as documented by signature changes in NMR and electronic absorption spectra, as well as by cyclic voltammetry, where two well-separated reversible redox couples were observed. EPR spectra of one-electron oxidized dimers closely mimic those of native special pairs, and strong through-space interactions between corrole subunits inferred from spectroscopic and electrochemical data are further supported by crystal structure analyses (3 Å interplanar distances, 5 Å lateral shifts, and 6 Å metal to metal distances).


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.1c02362DOIArticle
ORCID:
AuthorORCID
Sharma, Vinay K.0000-0002-2979-169X
Mahammed, Atif0000-0001-9042-9764
Mizrahi, Amir0000-0002-1376-0880
Morales, Maryann0000-0002-1778-8901
Fridman, Natalia0000-0001-8929-6829
Gray, Harry B.0000-0002-7937-7876
Gross, Zeev0000-0003-1170-2115
Additional Information:© 2021 American Chemical Society. Received: March 7, 2021; Published: May 20, 2021. This research was supported by the Israel-India Ministries of Science and Technology (2029941, Z.G.); work at Caltech was supported by the National Institute of Diabetes and Digestive and Kidney Diseases of the National Institutes of Health (R01-DK019038, HBG). Transient absorption spectra were collected in the Beckman Institute Laser Resource Center supported by the Arnold and Mabel Beckman Foundation. The content is solely the responsibility of the authors and does not necessarily represent official views of the National Institutes of Health. The authors declare no competing financial interest. Accession Codes. CCDC 2058315–2058318 contain the supplementary crystallographic data for this paper.
Funders:
Funding AgencyGrant Number
Ministry of Science and Technology (Israel)2029941
Department of Science and Technology (India)2029941
NIHR01-DK019038
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:Redox reactions, Oligomers, Aromatic compounds, Solvents, Imidazoles
Issue or Number:25
PubMed Central ID:PMC8249354
Record Number:CaltechAUTHORS:20210524-163212708
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210524-163212708
Official Citation:Dimeric Corrole Analogs of Chlorophyll Special Pairs. Vinay K. Sharma, Atif Mahammed, Amir Mizrahi, Maryann Morales, Natalia Fridman, Harry B. Gray, and Zeev Gross. Journal of the American Chemical Society 2021 143 (25), 9450-9460; DOI: 10.1021/jacs.1c02362
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109244
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 May 2021 15:03
Last Modified:26 Aug 2021 18:57

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