Boranes: The Boron Subhydride B_104.67H₃ with a Distorted β-Boron Crystal Structure

Abstract

A single crystal of the boron subhydride B 104.67(4) H 3 was serendipitously obtained while attempting to synthesize βboron. An accurate crystal structure analysis revealed a distorted βboron framework with the noncentrosymmetric space group R3m. We have found one interstitial site occupied by boron. The site related by inversion remains empty. The distortions of the framework result in ideal environments for the interstitial boron atom, and for the three hydrogen atoms at bridging positions between icosahedral B 12 groups, they result in ideal B−H distances of 1.33 Å. B 104.67(4) H 3 is a borane with the lowest amount of hydrogen recorded to date, and it is the first compound with a noncentrosymmetrically distorted β-boron framework.

First-Principles Calculations for the Impact of Hydrogenation on the Electron Behavior and Stability of Borophene Nanosheets: Implications for Boron 2D Electronics

“…25 The boron−hydrogen (BH) system is isoelectronic with carbon because a hydrogen atom can share electrons with a boron atom. 21,29,30 Such hydrogenation borophene nanosheets are expected to have excellent stability and unique properties such as the Dirac cone feature, 31 which are similar to graphene, silicene, and germanene. 32 The electron deficiency in the boron network can be stabilized by the possible formation of two-center-two-electron (2c-2e) and three-center-two-electron (3c-2e) bonds in the boron-hydride layer.…”

“…Chemical functionalization, − ribbon construction, and defect engineering are common methods to tailor the inherent properties of 2D materials and form new derivatives. ,,, Among them, chemical functionalization, especially hydrogenation and fluorination, can not only adjust the strength of interlayer interaction but also tune the electronic structure to switch them from a metal to a semiconductor, thus expanding their application range . The boron–hydrogen (BH) system is isoelectronic with carbon because a hydrogen atom can share electrons with a boron atom. ,, Such hydrogenation borophene nanosheets are expected to have excellent stability and unique properties such as the Dirac cone feature, which are similar to graphene, silicene, and germanene . The electron deficiency in the boron network can be stabilized by the possible formation of two-center-two-electron (2c-2e) and three-center-two-electron (3c-2e) bonds in the boron-hydride layer. , Motivated by this, the search for stable BH nanosheets with unique electronic structure has aroused great interest.…”