Unraveling hydridic-to-protonic dihydrogen bond predominance in monohydrated dodecaborate clusters

Yanrong Jiang; Qinqin Yuan; Wenjin Cao; Zhubin Hu; Yan Yang; Cheng Zhong; Tao Yang; Haitao Sun; Xue-Bin Wang; Zhenrong Sun

doi:10.1039/D2SC03986A

Unraveling hydridic-to-protonic dihydrogen bond predominance in monohydrated dodecaborate clusters†

Yanrong Jiang,‡^a Qinqin Yuan,‡^be Wenjin Cao,

^b Zhubin Hu,^a Yan Yang,

^a Cheng Zhong,^d Tao Yang,^a Haitao Sun,

*^ac Xue-Bin Wang

*^b and Zhenrong Sun*^ac

Author affiliations

* Corresponding authors

^a State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, Shanghai 200241, China
E-mail: htsun@phy.ecnu.edu.cn, zrsun@phy.ecnu.edu.cn

^b Physical Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P. O. Box 999, MS K8-88, Richland, Washington 99352, USA
E-mail: xuebin.wang@pnnl.gov

^c Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, Shanxi 030006, China

^d College of Chemistry & Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, China

^e Department of Chemistry, Anhui University, Hefei, Anhui, China

Abstract

Hydridic-to-protonic dihydrogen bonds (DHBs) are involved in comprehensive structural and energetic evolution, and significantly affect reactivity and selectivity in solution and solid states. Grand challenges exist in understanding DHBs’ bonding nature and strength, and how to harness DHBs. Herein we launched a combined photoelectron spectroscopy and multiscale theoretical investigation using monohydrated closo-dodecaborate clusters B₁₂X₁₂²⁻·H₂O (X = H, F, I) to address such challenges. For the first time, a consistent and unambiguous picture is unraveled demonstrating that B–H⋯H–O DHBs are superior to the conventional B–X⋯H–O HBs, being 1.15 and 4.61 kcal mol⁻¹ stronger than those with X = F and I, respectively. Energy decomposition analyses reveal that induction and dispersion terms make pronounced contributions resulting in a stronger B–H⋯H–O DHB. These findings call out more attention to the prominent roles of DHBs in water environments and pave the way for efficient and eco-friendly catalytic dihydrogen production based on optimized hydridic-to-protonic interactions.

Chemical Science

Unraveling hydridic-to-protonic dihydrogen bond predominance in monohydrated dodecaborate clusters†

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Unraveling hydridic-to-protonic dihydrogen bond predominance in monohydrated dodecaborate clusters

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