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Properties of perhalogenated {closo-B10} and {closo-B11} multiply charged anions and a critical comparison with {closo-B12} in the gas and the condensed phase

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c8cp05313h· OSTI ID:1542952
 [1];  [2];  [1];  [3];  [2];  [2];  [2];  [2];  [1];  [3];  [1];  [4];  [5];  [1];  [2]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Julius-Maximilians-Universität Würzburg (Germany)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  4. Purdue Univ., West Lafayette, IN (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
+ Show Author Affiliations
closo-Borate anions [closo-BnXn]2– are part of the most famous textbook examples of polyhedral compounds. Substantial differences in their reactivity and interactions with other compounds depending on the substituent X and cluster size n have been recognized, which favor specific closo-borates for different applications in cancer treatment, chemical synthesis, and materials science. Surprisingly, a fundamental understanding of the molecular properties underlying these differences is lacking. In this paper, we report our study comparing the electronic structure and reactivity of closo-borate anions [closo-BnXn]2– (X = Cl, Br, I, n = 10, 11, 12 in all combinations) in the gas phase and in solution. We investigated the free dianions and the ion pairs [nBu4N]+[closo-BnXn]2– by gas phase anion photoelectron spectroscopy accompanied by theoretical investigations. Strong similarities in electronic structures for n = 10 and 11 were observed, while n = 12 clusters were different. A systematic picture of the development in electronic stability along the dimension X is derived. Collision induced dissociation shows that fragmentation of the free dianions is mainly dependent on the substituent X and gives access to a large variety of boron-rich molecular ions. Fragmentation of the ion pair depends strongly on n. The results reflect the high chemical stability of clusters with n = 10 and 12, while those with n = 11 are much more prone to dissociation. We bridge our study to the condensed phase by performing comparative electrochemistry and reactivity studies on closo-borates in solution. The trends found at the molecular level are also reflected in the condensed-phase properties. We discuss how the gas phase values allow evaluation of the influence of the condensed phase on the electronic stability of closo-borates. A synthetic method via an oxidation/chlorination reaction yielding [closo-B10Cl10]2– from highly chlorinated {closo-B11} clusters is introduced, which underlines the intrinsically high reactivity of the {closo-B11} cage.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
Alexander von Humboldt Foundation; Deutsche Forschungsgemeinschaft (DFG); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1542952
Alternate ID(s):
OSTI ID: 1524162
OSTI ID: 1484540
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 11 Vol. 21; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Electrospray ionization photoelectron spectroscopy of cryogenic [EDTA·M( ii )] 2− complexes (M = Ca, V–Zn): electronic structures and intrinsic redox properties journal January 2019
A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B 12 H 12 ] 2− journal April 2019
Photoelectron spectroscopy of [Mo 6 X 14 ] 2− dianions (X = Cl–I) journal November 2019
Chemistry of 11-Vertex Polyhedral Boron Hydrides (Review) journal August 2019

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