Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence
Abstract
Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal MnIV oxidation state. The Soret maxima of Mn[TpXPC]Cl (TpXPC = meso-tris(p-X-phenyl)corrole, where X = CF3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[TpXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole•2–-like ligand for the MnCl complexes and an innocent corrole3– ligand for the MnPh complexes. Single-crystal X-ray structures of three Mn[TpXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[TpOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled MnIII-corrole•2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially MnIV-corrole3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[TpCF3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[TpCF3PC]Cl, consistent with a more oxidized,more »
- Authors:
-
- UiT- The Artic Univ. of Norway, Tromso (Norway)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of the Free State, Bloemfontein (Republic of South Africa)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1457057
- Grant/Contract Number:
- 231086; 262229; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 24; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ganguly, Sumit, MCormick, Laura J., Conradie, Jeanet, Gagnon, Kevin J., Sarangi, Ritimukta, and Ghosh, Abhik. Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.8b00537.
Ganguly, Sumit, MCormick, Laura J., Conradie, Jeanet, Gagnon, Kevin J., Sarangi, Ritimukta, & Ghosh, Abhik. Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence. United States. https://doi.org/10.1021/acs.inorgchem.8b00537
Ganguly, Sumit, MCormick, Laura J., Conradie, Jeanet, Gagnon, Kevin J., Sarangi, Ritimukta, and Ghosh, Abhik. Wed .
"Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence". United States. https://doi.org/10.1021/acs.inorgchem.8b00537. https://www.osti.gov/servlets/purl/1457057.
@article{osti_1457057,
title = {Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence},
author = {Ganguly, Sumit and MCormick, Laura J. and Conradie, Jeanet and Gagnon, Kevin J. and Sarangi, Ritimukta and Ghosh, Abhik},
abstractNote = {Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal MnIV oxidation state. The Soret maxima of Mn[TpXPC]Cl (TpXPC = meso-tris(p-X-phenyl)corrole, where X = CF3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[TpXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole•2–-like ligand for the MnCl complexes and an innocent corrole3– ligand for the MnPh complexes. Single-crystal X-ray structures of three Mn[TpXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[TpOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled MnIII-corrole•2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially MnIV-corrole3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[TpCF3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[TpCF3PC]Cl, consistent with a more oxidized, i.e., MnIV, center in Mn[TpCF3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[TpCF3PC]Ph results from the extra 3dz2 hole, which mixes strongly with the Mn 4pz orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[TpXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.},
doi = {10.1021/acs.inorgchem.8b00537},
journal = {Inorganic Chemistry},
number = 24,
volume = 56,
place = {United States},
year = {Wed Jun 06 00:00:00 EDT 2018},
month = {Wed Jun 06 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
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