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

A multitude of applications related to perhydroxylated closo -dodecaborate B 12 (OH) 12 2- in the condensed phase are inseparable from the fundamental mechanisms underlying the high water orientation selectivity based on the base B 12 (OH) 12 2- . Herein, we directly compare the structural evolution of water clusters, ranging from monomer to hexamer, oriented by functional groups in the bases B 12 H 12 2- , B 12 H 11 OH 2- and B 12 (OH) 12 2- using multiple theoretical methods. A significant revelation is made regarding B 12 (OH) 12 2- : 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 B 12 H 12 2- and B 12 H 11 OH 2- 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 B 12 (OH) 12 2- . 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.