Design of chemical Reactions based on the Crystal Structures

X射线晶体学家、有机化学家和物理化学家共同研究了晶体结构与反应机理之间的关系。利用晶场进行分子设计和化学反应控制，获得了许多有趣的结果。1.手性主体化合物有效的光学拆分被发现和手性光反应的结晶包合物被控制（户田）。利用X射线衍射（Ohashi）研究了钴肟配合物的晶态反应和光异构化反应.基于X射线结构分析，证明了环糊精和β-联萘的选择性包合现象（Fujiwara）。用X射线衍射法研究了合成的丝光沸石的晶体结构，用红外光谱（Ito）观察了乙烯在丝光沸石上的吸附行为.表面分子的取向和反应进行了研究，通过潘宁电离电子能谱（原田）。利用高分辨电子显微镜（小林）直接观察了碘掺杂引起聚酞菁拓扑结构的形成和结构变化的机理.在X射线结构分析（Kai）的基础上研究了辐射诱导聚合的机制以及酶与其底物的相互作用。进行了新的金属CT配合物、多阶段氧化还原体系的分子设计和结构分析（Nakasuji）。基于X射线结构分析，研究了高价硫化合物中通过高价中间体和分子间或分子内相互作用的反应路径（岩崎）.利用分子力学（Osawa）进行天然产物的分子设计。用Hosoya的从头算分子轨道对氧化数和电子结构进行了量子化学解释.

Relationships between crystal structures and reaction mechanism were studied cooperatively by X-ray Crystallographers, organic chemists and physical chemists. Many interesting results were obtained about the molecular design and the control of chemical ractions by use of the crystalline field.1. Chiral host compounds effective for optical resolution were found and chiral photoreactions in crystalline inclusion complexes were controlled (Toda). Crystalline-state reaction and - photoisomerization of cobaloxime complexes were studied by X-ray analysis (Ohashi).2. Based on X-ray structure analysis selective inclusion phenomena of cyclodextrins and -binaphthol were demonstrated (Fujiwara). The crystal structure of the synthetic moldenite was studied by an X-ray method and a behavior of the adsorbed ethylene on mordenite was observed by IR spectra (Ito).3. Orientation of surface molecules and reactions were investigated by Penning ionization electron spectroscopy (Harada). The mechanism of the topotactic formation and structure change in polyphthalocyanine caused by iodine doping were observed directly by high-resolution electron microscopy (Kobayashi).4. The mechanism of polymerization induced by irradiation and the interaction of enzymes with thier substrates were studied on the bases of X-ray structure analysis (Kai). The molecular design for new metallic CT complexes, multi-stage redox system, and the structure analysis were carried out (Nakasuji). Based on the X-ray structure analysis reaction paths via hypervalent intermediates and inter- or intramolecular interactin in the hypervalent sulfur compounds were investigated (Iwasaki).5. Molecular design for natural products was carried out by use of molecular mechanics (Osawa). Quantum chemical interpretation of oxidation number and -electronic structure was made with ab initio molecular orbitals (Hosoya).