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Title: Metallo-boranes: a class of unconventional superhalogens defying electron counting rules

Journal Article · · Nanoscale
DOI:https://doi.org/10.1039/D1NR06929B· OSTI ID:1838561
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Physics Department, Virginia Commonwealth University, Richmond, VA 23284, USA
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Superhalogens are a class of highly electronegative atomic clusters whose electron affinities exceed those of halogens. Due to their potential for promoting unusual reactions and role as weakly coordinating anions as well as building blocks of bulk materials, there has been considerable interest in their design and synthesis. Conventional superhalogens are composed of a metal atom surrounded by halogen atoms. Their large electron affinities are due to the fact that the added electron is distributed over all the halogen atoms, reducing electron–electron repulsion. Here, using density functional theory with a hybrid exchange–correlation functional, we show that a new class of superhalogens can be developed by doping closo-boranes (e.g., B12H12) with selected metal atoms such as Zn and Al as well as by replacing a B atom with Be or C. Strikingly, these clusters defy electron counting rules. For example, according to the Wade–Mingos rule, Zn(B12H12) and Al(BeB11H12) are closed-shell systems that should be chemically inert and, hence, should have very small electron affinities. Similarly, Zn(B12H11), Al(B12H12), and Zn(CB11H12), with one electron more than needed for electronic shell closure, should behave like superalkalis. Yet, all these clusters are superhalogens. This unexpected behavior originates from an entirely different mechanism where the added electron resides on the doped metal atom that is positively charged due to electron transfer.

Research Organization:
Virginia Commonwealth Univ., Richmond, VA (United States); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)
Grant/Contract Number:
FG02-96ER45579; AC02-05CH11231
OSTI ID:
1838561
Alternate ID(s):
OSTI ID: 1978813
Journal Information:
Nanoscale, Journal Name: Nanoscale Vol. 14 Journal Issue: 5; ISSN 2040-3364
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English

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