Sigmund Lukas M, Maier Rouven, Greb Lutz
Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg Germany
Department of Chemistry and Biochemistry - Inorganic Chemistry, Freie Universität Berlin Fabeckstr. 34/36 14195 Berlin Germany.
Chem Sci. 2021 Dec 15;13(2):510-521. doi: 10.1039/d1sc05395g. eCollection 2022 Jan 5.
The tetrahedron is the primary structural motif among the p-block elements and determines the architecture of our bio- and geosphere. However, a broad understanding of the configurational inversion of tetrahedral compounds is missing. Here, we report over 250 energies (DLPNO-CCSD(T)) for square planar inversion of third- and fourth-period element species of groups 13, 14, and 15. Surprisingly low inversion barriers are identified for compounds of industrial relevance (, ≈100 kJ mol for Al(OH) ). More fundamentally, the second-order Jahn-Teller theorem is disclosed as suitable to rationalize substituent and central element effects. Bond analysis tools give further insights into the preference of eight valence electron systems with four substituents to be tetrahedral. Hence, this study develops a model to understand, memorize, and predict the angular flexibility of tetrahedral species. Perceiving the tetrahedron not as forcingly rigid but as a dynamic structural entity might leverage new approaches and visions for adaptive matter.
四面体是p区元素中的主要结构单元，决定了我们生物和地球圈层的结构。然而，目前对四面体化合物构型反转缺乏广泛的理解。在此，我们报告了第13、14和15族第三和第四周期元素物种平面正方形反转的250多个能量（DLPNO-CCSD(T)）。令人惊讶的是，对于具有工业相关性的化合物（如Al(OH)₃，反转势垒约为100 kJ/mol），其反转势垒很低。更重要的是，二阶 Jahn-Teller 定理被证明适用于解释取代基和中心元素的影响。键分析工具进一步深入了解了具有四个取代基的八价电子体系倾向于形成四面体的原因。因此，本研究建立了一个模型，用于理解、记忆和预测四面体物种的角灵活性。将四面体视为并非强制刚性而是动态结构实体，可能会为适应性物质带来新的方法和愿景。
