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A Super-Oxidized Radical Cationic Icosahedral Boron Cluster

Stauber, Julia M. and Schwan, Josef and Zhang, Xinglong and Axtell, Jonathan C. and Jung, Dahee and McNicholas, Brendon J. and Oyala, Paul H. and Martinolich, Andrew J. and Winkler, Jay R. and See, Kimberly A. and Miller, Thomas F., III and Gray, Harry B. and Spokoyny, Alexander M. (2020) A Super-Oxidized Radical Cationic Icosahedral Boron Cluster. Journal of the American Chemical Society, 142 (30). pp. 12948-12953. ISSN 0002-7863. doi:10.1021/jacs.0c06159.

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While the icosahedral closo-[B₁₂H₁₂]²⁻ cluster does not display reversible electrochemical behavior, perfunctionalization of this species via substitution of all 12 B–H vertices with alkoxy or benzyloxy (OR) substituents engenders reversible redox chemistry, providing access to clusters in the dianionic, monoanionic, and neutral forms. Here, we evaluated the electrochemical behavior of the electron-rich B₁₂(O-3-methylbutyl)₁₂ (1) cluster and discovered that a new reversible redox event that gives rise to a fourth electronic state is accessible through one-electron oxidation of the neutral species. Chemical oxidation of 1 with [N(2,4-Br₂C₆H₃)₃]·⁺ afforded the isolable [1]·⁺ cluster, which is the first example of an open-shell cationic B₁₂ cluster in which the unpaired electron is proposed to be delocalized throughout the boron cluster core. The oxidation of 1 is also chemically reversible, where treatment of [1]·⁺ with ferrocene resulted in its reduction back to 1. The identity of [1]·⁺ is supported by EPR, UV–vis, multinuclear NMR (¹H, ¹¹B), and X-ray photoelectron spectroscopic characterization.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Stauber, Julia M.0000-0001-9783-907X
Schwan, Josef0000-0002-1086-6698
Zhang, Xinglong0000-0003-1698-692X
Axtell, Jonathan C.0000-0002-5579-4296
Jung, Dahee0000-0003-1863-0193
McNicholas, Brendon J.0000-0002-3654-681X
Oyala, Paul H.0000-0002-8761-4667
Martinolich, Andrew J.0000-0002-7866-9594
Winkler, Jay R.0000-0002-4453-9716
See, Kimberly A.0000-0002-0133-9693
Miller, Thomas F., III0000-0002-1882-5380
Gray, Harry B.0000-0002-7937-7876
Spokoyny, Alexander M.0000-0002-5683-6240
Additional Information:© 2020 American Chemical Society. Received: June 8, 2020; Published: July 10, 2020. 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 No. DE-SC0019381 (A.M.S. and K.A.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. Acknowledgment is made to the donors of The American Chemical Society Petroleum Research Fund for funding work in the H.B.G. lab (J.S. and H.B.G.). Work in the Beckman Institute at Caltech was supported by the Arnold and Mabel Beckman Foundation (B.J.M., J.R.W.). X.Z. acknowledges the Agency for Science, Technology and Research (Singapore) for an A*STAR fellowship. 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. A.J.M. acknowledges support through a postdoctoral fellowship from the Resnick Sustainability Institute at Caltech. D.J. acknowledges the UCLA Graduate Division for the Dissertation Year Fellowship. The National Science Foundation (NSF-1531940) and the Dow Next Generation Educator Fund are acknowledged for EPR facility support. The authors declare the following competing financial interest(s): UCLA has patents on several compounds reported in this work from which A.M.S. and current/former co-workers may receive royalty payments. The Cs₂[B₁₂(OH)₁₂] salt (Catalog #902209) is commercially available through the MilliporeSigma catalog.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0019381
Cottrell Scholar of Research CorporationUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Issue or Number:30
Record Number:CaltechAUTHORS:20200713-085326752
Persistent URL:
Official Citation:A Super-Oxidized Radical Cationic Icosahedral Boron Cluster. Julia M. Stauber, Josef Schwan, Xinglong Zhang, Jonathan C. Axtell, Dahee Jung, Brendon J. McNicholas, Paul H. Oyala, Andrew J. Martinolich, Jay R. Winkler, Kimberly A. See, Thomas F. Miller, Harry B. Gray, and Alexander M. Spokoyny. Journal of the American Chemical Society 2020 142 (30), 12948-12953; DOI: 10.1021/jacs.0c06159
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:104347
Deposited By: Tony Diaz
Deposited On:13 Jul 2020 19:03
Last Modified:01 Jun 2023 22:44

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