当前位置：
X-MOL 学术
›
Inorg. Chem. Front.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Pyramidal inversion in the solid state
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2024-07-26 , DOI: 10.1039/d4qi01021c Robin Turnbull 1 , Javier Gonzalez Platas 2 , Alfonso Muñoz 3 , Josu Sánchez-Martín 1 , M. Jasmin 4 , Gaston Garbarino 5 , Daniel Errandonea 1 , Akun Liang 1
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2024-07-26 , DOI: 10.1039/d4qi01021c Robin Turnbull 1 , Javier Gonzalez Platas 2 , Alfonso Muñoz 3 , Josu Sánchez-Martín 1 , M. Jasmin 4 , Gaston Garbarino 5 , Daniel Errandonea 1 , Akun Liang 1
Affiliation
|
Pyramidal inversion is a stereochemical phenomenon that describes the interconversion between two equivalent pyramidal configurations of the same chemical species. Using the IO3 molecule as a prototypical trigonal pyramidal unit, pyramidal inversion has been observed in the solid state by applying hydrostatic pressure to crystals of barium di-iodate monohydrate, Ba(IO3)2·H2O, without chemical reaction or the introduction/elimination of guest molecules. The pyramidal inversion was identified by high-pressure single-crystal synchrotron X-ray diffraction from the appearance of charge density on the unoccupied side of the IO3 pyramid at pressures above 5 GPa. The percentage of inverted pyramids increases with pressure, from 2.5% at 5.10(5) GPa to 17.5% at 14.84(5) GPa. The energetic competition between the original and inverted IO3 pyramids as a function of pressure is investigated by density functional theory calculations, finding the two configurations to be very close in energy. Factors contributing to the observation of pyramidal inversion in barium iodate monohydrate are discussed and it is suggested that hydrogen bonding due to the presence of water may play a significant role.
中文翻译：
固态金字塔反转
金字塔反转是一种立体化学现象，描述相同化学物质的两个等效金字塔构型之间的相互转化。使用IO 3分子作为典型的三角锥体单元，通过对二碘酸钡一水合物Ba(IO 3 ) 2 ·H 2 O晶体施加静水压，在固态下观察到锥体反转，无需化学反应或客体分子的引入/消除。通过高压单晶同步加速器 X 射线衍射，根据 IO 3金字塔未占据一侧在压力高于 5 GPa 的情况下出现的电荷密度，确定了金字塔反转。倒金字塔的百分比随着压力的增加而增加，从 5.10(5) GPa 时的 2.5% 到 14.84(5) GPa 时的 17.5%。通过密度泛函理论计算研究了原始 IO 3金字塔和倒置 IO 3 金字塔之间作为压力函数的能量竞争，发现两种构型的能量非常接近。讨论了有助于在一水合碘酸钡中观察到锥体倒转的因素，并表明由于水的存在而产生的氢键可能发挥重要作用。
更新日期：2024-07-26
中文翻译：
固态金字塔反转
金字塔反转是一种立体化学现象，描述相同化学物质的两个等效金字塔构型之间的相互转化。使用IO 3分子作为典型的三角锥体单元，通过对二碘酸钡一水合物Ba(IO 3 ) 2 ·H 2 O晶体施加静水压，在固态下观察到锥体反转，无需化学反应或客体分子的引入/消除。通过高压单晶同步加速器 X 射线衍射，根据 IO 3金字塔未占据一侧在压力高于 5 GPa 的情况下出现的电荷密度，确定了金字塔反转。倒金字塔的百分比随着压力的增加而增加，从 5.10(5) GPa 时的 2.5% 到 14.84(5) GPa 时的 17.5%。通过密度泛函理论计算研究了原始 IO 3金字塔和倒置 IO 3 金字塔之间作为压力函数的能量竞争，发现两种构型的能量非常接近。讨论了有助于在一水合碘酸钡中观察到锥体倒转的因素，并表明由于水的存在而产生的氢键可能发挥重要作用。
京公网安备 11010802027423号