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Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters

Li, Bo and Zhang, Xinglong and Stauber, Julia M. and Miller, Thomas F., III and Spokoyny, Alexander M. (2021) Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters. Journal of Physical Chemistry A, 125 (28). pp. 6141-6150. ISSN 1089-5639. doi:10.1021/acs.jpca.1c03927.

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The expanding field of boron clusters has attracted continuous theoretical efforts to understand their diverse structures and unique bonding. We recently discovered a new reversible redox event of B₁₂(O-3-methylbutyl)₁₂ in which the superoxidized radical cationic form [B₁₂(O-3-methylbutyl)₁₂]•+ was identified and isolated for the first time. Herein, comprehensive (TD-)DFT studies in tandem with electrochemical experiments were employed to demonstrate the generality of the reported behavior across perfunctionalized B₁₂(OR)₁₂ clusters (R = aryl or alkyl). While the spin density of radical cationic clusters is delocalized in the core region, the oxidation brings about notable gains of positive partial charges on the supporting groups whose electronics can readily tune the redox potential of the 0/•+ couple. The underlying changes of frontier orbitals were elucidated, and the resulting [B₁₂(OR)₁₂]•+ species manifest a general diagnostic absorption as a consequence of mixed local/charge-transfer excitations.

Item Type:Article
Related URLs:
URLURL TypeDescription
Zhang, Xinglong0000-0003-1698-692X
Stauber, Julia M.0000-0001-9783-907X
Miller, Thomas F., III0000-0002-1882-5380
Spokoyny, Alexander M.0000-0002-5683-6240
Additional Information:© 2021 American Chemical Society. Received: May 2, 2021; Revised: June 15, 2021; Published: July 9, 2021. This work was supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DE-SC0019381 (A.M.S. synthesis and characterization; T.F.M., computational work and theory). A.M.S. is a Research Corporation for Science Advancement (RCSA) Cottrell Scholar and a Dreyfus Foundation Camille Dreyfus Teacher-Scholar. X.Z. acknowledges the Agency for Science, Technology and Research (Singapore) for a National Science Scholarship (NSS-PhD) funding. B.L., X.Z., and T.F.M. acknowledge the computational resources from the Extreme Science and Engineering Discovery Environment (XSEDE) Bridges computer at the Pittsburgh Supercomputing Center through allocation TG-MCB160013. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0019381
Cottrell Scholar of Research CorporationUNSPECIFIED
Henry and Camille Dreyfus FoundationUNSPECIFIED
Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
Subject Keywords:Redox reactions, Substituents, Boron, Quantum mechanics, Cluster chemistry
Issue or Number:28
Record Number:CaltechAUTHORS:20210721-172302557
Persistent URL:
Official Citation:Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters. Bo Li, Xinglong Zhang, Julia M. Stauber, Thomas F. Miller, and Alexander M. Spokoyny. The Journal of Physical Chemistry A 2021 125 (28), 6141-6150; DOI: 10.1021/acs.jpca.1c03927
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109954
Deposited By: Tony Diaz
Deposited On:26 Jul 2021 22:41
Last Modified:05 Aug 2021 16:50

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