上海科技大学知识管理系统

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 (OH-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-HH-O), conventional hydrogen bonds (B-(H-O)H-O) and water hydrogen bonds (OH-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. © 2023 The Royal Society of Chemistry.