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Beyond Duality: Rationalizing Repulsive Coulomb Barriers in Host–Guest Cyclodextrin–Dodecaborate Complexes

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [2];  [3];  [4];  [5];  [2];  [6]
  1. East China Normal Univ. (ECNU), Shanghai (China); ShanghaiTech Univ. (China)
  2. East China Normal Univ. (ECNU), Shanghai (China)
  3. ShanghaiTech Univ. (China)
  4. Wuhan Univ. (China)
  5. East China Normal Univ. (ECNU), Shanghai (China); Shanxi Univ., Taiyuan (China); New York University Shanghai (China)
  6. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
+ Show Author Affiliations
The repulsive Coulomb barrier (RCB), an intrinsic potential energy barrier along electron detachment or charge-separation coordinates in multiply charged anions (MCAs), provides dynamic stability to MCAs whose electronic and thermodynamic stabilities are largely dictated by strong internal Coulomb repulsions. Spectroscopic and theoretical characterizations of the RCB have been focused on isolated MCAs. In this work, we extend the RCB investigation beyond the previous scope by including noncovalent host–guest cyclodextrin-closo-dodecaborate dianionic complexes χCD·B12X122–(χ = α, β, γ; X = H, F–I). Here, photodechment photoelectron spectroscopy reveals the existence of two distinctly different RCBs, derived from detaching electrons from the guest dianions (RCB1) or ionizing the host neutrals (RCB2), respectively, with the latter being substantially smaller than the former. In conclusion, theoretical calculations support the duality of RCBs in these complexes and further exhibit highly anisotropic nature of the RCBs.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2035567
Report Number(s):
PNNL-SA--185596
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 30 Vol. 14; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anions
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electrostatic potential
polarization
potential energy