单一混合共晶系统中的不同堆叠类型: π···π-和 π-孔基有机-无机平面组件
Sergey V Baykov1, Eugene A Katlenok1, Artem V Semenov1
1Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg 199034, Russian Federation.
Inorganic chemistry
|February 20, 2025
概括
这项研究揭示,复合物与缺乏电子的芳化合物相互作用不同,表现出由各种非对应力驱动的独特堆叠行为. 这一发现对于设计新型混合材料至关重要.
科学领域:
- 超分子化学 超分子化学
- 晶体工程 晶体工程
- 有机金属化学 有机金属化学
背景情况:
- 平面双化复合体可以与缺乏电子的芳香分子形成共晶体.
- 了解非共价相互作用是控制晶体结构和材料特性的关键.
研究的目的:
- 为了研究不同缺电子芳香物:六二 (C6F6) 和1,2,4,5-四二 (TCB) 的复合物 ([Pd(NO) 2)) 的独特堆叠模式.
- 阐明这些不同的堆叠行为所支配的潜在的非共价相互作用机制.
主要方法:
- 与C6F6和TCB共结晶的复合物.
- 得到的共晶体 (1·3(C6F6) 和1·2TCB) 的X射线衍射分析.
- 计算分析包括原子在分子中的量子理论 (QTAIM),基于希尔什菲尔德分区 (IGMH) 的独立梯度模型,带有电荷移位函数的化学价值理论的扩展过渡状态自然轨道 (ETS-NOCV/CDF) 和对称适应扰动理论 (SAPT).
主要成果:
- 同晶1·3(C6F6) 和1·2TCB呈现不同的颜色和堆叠模式.
- 堆叠在1·3 ((C6F6) 中是由分子间偏振和分散力 (吸引能量的70%左右) 主导的,电荷转移最小.
- 在1·2TCB中堆叠的特点是显著的电荷转移 (35 me) 和感应元件,表明π孔相互作用.
结论:
- 复合体表现出两种与缺电子芳化合物的明显的分子间相互作用模式:π···π堆叠和电荷转移π孔相互作用.
- 在共晶体中,看似相似的结构图案可以从根本上不同的非对应力的组合中产生.
- 这些发现为混合有机-无机材料的合理设计和晶体工程提供了关键的见解.
相关概念视频
Metallic Solids
18.2K
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
18.2K
Ionic Crystal Structures
14.1K
Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
14.1K
Hybridization of Atomic Orbitals II
31.7K
sp3d and sp3d 2 Hybridization
31.7K
Crystal Field Theory - Tetrahedral and Square Planar Complexes
41.2K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
41.2K
Hybridization of Atomic Orbitals I
46.3K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
46.3K
π Molecular Orbitals of the Allyl Cation and Anion
4.0K
An allyl group is a three-carbon conjugated system where the sp³-hybridized allylic carbon is bonded to a CH=CH2 group via a single bond. Allyl anions can be obtained by treating propene with a strong base that can deprotonate methyl groups. Allyl cations are formed as intermediates during substitution reactions involving allylic halides. In both cases, the hybridization of the allylic carbon changes from sp3 to sp2, giving rise to a carbon chain with three sp2-hybridized carbons, each with...
4.0K


