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

作者：Jiang, Yanrong; Hu, Zhubin; Zhong, Cheng; Yang, Yan; Wang, Xue-Bin; Sun, Zhenrong; Sun, Haitao^*; Liu, Zhi^*; Peng, Peng^*

来源：Physical Chemistry Chemical Physics, 2023, 25(37): 25810-25817.

DOI：10.1039/d3cp03555g

• 3-DIMENSIONAL AROMATICITY
• ELECTRONIC-STRUCTURE
• CLUSTERS
• ANIONS
• SPECTROSCOPY
• COMPLEXES

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 B12H122-, B12H11OH2- 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)center dot center dot center dot H-O interactions prevail over the competition from water-hydrogen bonds (O center dot center dot center dot 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 center dot center dot center dot H-O), conventional hydrogen bonds (B-(H-O)center dot center dot center dot H-O) and water hydrogen bonds (O center dot center dot center dot 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.

• 单位
  武汉大学