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Locking water molecules via ternary O–H⋯O intramolecular hydrogen bonds in perhydroxylated closo-dodecaborate

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/D3CP03555G· OSTI ID:2572437
 [1];  [2];  [3];  [2];  [4];  [2];  [2];  [5];  [5]
  1. ShanghaiTech Univ. (China); East China Normal Univ. (ECNU), Shanghai (China)
  2. East China Normal Univ. (ECNU), Shanghai (China)
  3. Wuhan Univ. (China)
  4. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  5. ShanghaiTech Univ. (China)
+ Show Author Affiliations
A multitude of applications related to perhydroxylated closo-dodecaborate B12(OH)122− in the condensed phase are inseparable from the fundamental mechanisms underlying the high water orientation selectivity based on the base B12(OH)122−. Herein, we directly compare the structural evolution of water clusters, ranging from monomer to hexamer, oriented by functional groups in the bases B12H122−, B12H11OH2− and B12(OH)122− using multiple theoretical methods. A significant revelation is made regarding B12(OH)122−: each additional water molecule is locked into the intramolecular hydrogen bond B–O–H ternary ring in an embedded form. This new pattern of water cluster growth suggests that B–(H–O)⋯H–O interactions prevail over the competition from water–hydrogen bonds (O⋯H–O), distinguishing it from the behavior observed in B12H122− and B12H11OH2− bases, in which competition arises from a mixed competing model involving dihydrogen bonds (B–H⋯H–O), conventional hydrogen bonds (B–(H–O)⋯H–O) and water hydrogen bonds (O⋯H–O). Through aqueous solvation and ab initio molecular dynamics analysis, we further demonstrate the largest water clusters in the first hydrated shell with exceptional thermodynamic stability around B12(OH)122−. These findings provide a solid scientific foundation for the design of boron cluster chemistry incorporating hydroxyl-group-modified borate salts with potential implications for various applications.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2572437
Alternate ID(s):
OSTI ID: 2001021
Report Number(s):
PNNL-SA--190035
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 37 Vol. 25; ISSN 1463-9076; ISSN 1463-9084
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY