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Published June 30, 2021 | Accepted Version + Supplemental Material
Journal Article Open

Dimeric Corrole Analogs of Chlorophyll Special Pairs

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).

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.

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Accepted Version - nihms-1711398.pdf

Supplemental Material - ja1c02362_si_001.pdf

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Additional details

Created:
August 20, 2023
Modified:
October 23, 2023