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. https://resolver.caltech.edu/CaltechAUTHORS:20200713-085326752
![[img]](https://authors.library.caltech.edu/style/images/fileicons/application_pdf.png) |
PDF
- Accepted Version
See Usage Policy. 1MB |
|
PDF
- Submitted Version
Creative Commons Attribution Non-commercial No Derivatives. 2MB |
|
PDF (Experimental procedures and characterization data for all new compounds)
- Supplemental Material
See Usage Policy. 3MB |
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20200713-085326752
Abstract
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: |
| ||||||||||||||||||||||||||||
| ORCID: |
| ||||||||||||||||||||||||||||
| 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 | ||||||||||||||||||||||||||||
| Funders: |
| ||||||||||||||||||||||||||||
| Issue or Number: | 30 | ||||||||||||||||||||||||||||
| DOI: | 10.1021/jacs.0c06159 | ||||||||||||||||||||||||||||
| Record Number: | CaltechAUTHORS:20200713-085326752 | ||||||||||||||||||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20200713-085326752 | ||||||||||||||||||||||||||||
| 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 | ||||||||||||||||||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||||||||||||||||||
| Deposited By: | Tony Diaz | ||||||||||||||||||||||||||||
| Deposited On: | 13 Jul 2020 19:03 | ||||||||||||||||||||||||||||
| Last Modified: | 01 Jun 2023 22:44 |
Repository Staff Only: item control page
