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Electronic Structures of Group 9 Metallocorroles with Axial Ammines

Dong, Sijia S. and Nielsen, Robert J. and Palmer, Joshua H. and Gray, Harry B. and Gross, Zeev and Dasgupta, Siddharth and Goddard, William A., III (2011) Electronic Structures of Group 9 Metallocorroles with Axial Ammines. Inorganic Chemistry, 50 (3). pp. 764-770. ISSN 0020-1669.

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The electronic structures of metallocorroles (tpfc)M(NH_3)_2 and (tfc)M(NH_3)_2 (tpfc is the trianion of 5,10,15-(tris)pentafluorophenylcorrole, tfc is the trianion of 5,10,15-trifluorocorrole, and M = Co, Rh, Ir) have been computed using first principles quantum mechanics [B3LYP flavor of Density Functional Theory (DFT) with Poisson−Boltzmann continuum solvation]. The geometry was optimized for both the neutral systems (formal M^(III) oxidation state) and the one-electron oxidized systems (formally M^(IV)). As expected, the M^(III) systems have a closed shell d^6 configuration; for all three metals, the one-electron oxidation was calculated to occur from a ligand-based orbital (highest occupied molecular orbital (HOMO) of B_1 symmetry). The ground state of the formal M^(IV) system has M^(III)-Cπ character, indicating that the metal remains d^6, with the hole in the corrole π system. As a result the calculated M^(IV/III) reduction potentials are quite similar (0.64, 0.67, and 0.56 V vs SCE for M = Ir, Rh and Co, respectively), whereas the differences would have been large for purely metal-based oxidations. Vertically excited states with substantial metal character are well separated from the ground state in one-electron-oxidized cobalt (0.27 eV) and rhodium (0.24 eV) corroles, but become closer in energy in the iridium (0.15 eV) analogues. The exact splittings depend on the chosen functional and basis set combination and vary by ~0.1 eV.

Item Type:Article
Related URLs:
URLURL TypeDescription
Dong, Sijia S.0000-0002-5811-9333
Nielsen, Robert J.0000-0002-7962-0186
Gray, Harry B.0000-0002-7937-7876
Dasgupta, Siddharth0000-0002-9161-7457
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2011 American Chemical Society. Published In Issue February 07, 2011. Article ASAP January 07, 2011. Received March 29, 2010. This work was supported by an NSF Center for Chemical Innovation (CCI Powering the Planet, Grants CHE-0802907 and CHE-0947829), the U.S.-Israel BSF (Z.G. and H.B.G.), CCSER (Gordon and Betty Moore Foundation), and the Arnold and Mabel Beckman Foundation. W.A.G. and R.S.N. and the quantum mechanicals calculations were supported as part of the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001298. S.S.D. was also supported by the Overseas Research Fellowship Scheme from the Faculty of Science, University of Hong Kong.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Binational Science Foundation (USA-Israel)UNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Department of Energy (DOE)DE-SC000-1298
University of Hong KongUNSPECIFIED
Issue or Number:3
Record Number:CaltechAUTHORS:20110404-100258063
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Official Citation:Electronic Structures of Group 9 Metallocorroles with Axial Ammines Sijia S. Dong, Robert J. Nielsen, Joshua H. Palmer, Harry B. Gray, Zeev Gross, Siddharth Dasgupta, and William A. Goddard, III pp 764–770 Publication Date (Web): January 7, 2011 (Article) DOI: 10.1021/ic1005902
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23227
Deposited By: Ruth Sustaita
Deposited On:19 Apr 2011 17:44
Last Modified:09 Mar 2020 13:18

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