Charge Density Level Structure of Molecular Doped Functional Nano Coordination Space

利用SPring-8高亮度同步加速器气体吸附原位粉末衍射实验和MEM（最大熵法）/Rietveld电荷密度分析，研究了纳米配位空间和吸附分子的精确晶体结构，包括电子密度。精确的结构信息将使我们了解主框架和客体分子在纳米配位空间中的相互作用机制。我们揭示了多孔配位聚合物的各种晶体结构与气体分子的吸附。在CPL-1上吸附氢时，可以清楚地观察到被吸附氢分子在纳米通道中的电子密度。结果表明，金属-氧单元与氢分子有吸引力的相互作用位点相关联，孔壁上与氢分子大小相适应的空腔对有效的氢离子调节很重要。发现CPL-1在室温下储存的乙炔密度极高，超过了安全压缩极限。从MEM电荷密度来看，乙炔分子与孔壁上的氧原子被双氢键捕获。此外，还首次发现了乙炔吸附的中间吸附态。在整个吸附现象中有关结构变化的信息是非常重要的，并且对于多孔框架的可行设计是必需的。最近，基于MEM电荷密度的静电势被开发出来，并被发现有助于理解客体和主体框架之间的分子间相互作用。本项目所获得的精确结构信息对于理解纳米配位空间中的气体吸附现象具有重要意义。为新型多孔配位聚合物功能材料的设计和合理的合成策略提供了理论依据。少

The aim of our research is to determine the precise crystal structure, including the electron densities, of nano-coordination space and adsorbed molecules by an in situ powder diffraction experiment of gas adsorption using high brilliance synchrotron light source at SPring-8 and the MEM(maximum entropy method)/Rietveld charge density analysis. Precise structural information will allow us to understand the interaction mechanism between the host framework and guest molecules in the nano-coordination space. We have revealed various crystal structures of porous coordination polymers with the adsorption of gas molecules.In hydrogen adsorption on CPL-1, the electron densities of adsorbed hydrogen molecules were clearly observed in the nanochannels. It was suggested from the result that the metal-oxygen unit is associated with an attractive interaction site for hydrogen molecules and the cavity on the pore wall well-suited to the size of hydrogen molecule is important for the effective hydrog … More en accommodation.CPL-1 was found to store acetylene with extremely high density beyond the safety compression limit at room temperature. From the MEM charge density, acetylene molecule was found to be trapped by double hydrogen bonds with the oxygen atoms on the pore wall. Furthermore, an intermediate adsorption state was also revealed for acetylene adsorption for the first time. The information on structural changes throughout the adsorption phenomena is very important and required for a feasible design of a porous framework.Recently, the electrostatic potential based on the MEM charge density was developed and was found to be useful for understanding intermolecular interaction between guest and host framework.The precise structural information obtained in this project is important for the understanding of gas adsorption phenomena in the nano-coordination space. It will also contribute to the design and the rational synthetic strategy of novel porous coordination Polymers as functional materials. Less