Functionalization and Control of Structure of Crystals of Interacting Molecules.

该项目的目的是发展分子间相互作用和多点相互作用的认识，这些相互作用控制着有机金属和有机晶体的晶体结构，并制备相关的新化合物。研究结果总结如下：1。利用金属-金属键和有机π体系，开发了一种具有新立体构型的新型电子共轭体系。一个例子是含有4个桥接芳香配体的钯簇配合物。阳离子自由基盐的晶体结构表现为三维相互作用网络的形成。2. 在胆酸及其衍生物的包合物中，宿主分子能够动态识别宿主官能团发生构象变化的目标分子。3. 合成了硫代羧酸、硒代羧酸和端氨基羧酸的新衍生物，并对其晶体结构进行了分析。4. 研究了10族均相催化剂催化合成硅烷和锡烷的方法，并对催化中间体的一些模型配合物的结构进行了分析。5. 对有机磷腈的液晶相进行了分析。6. 制备了由10和11族配合物形成的新超分子，并对其x射线结构进行了分析。根据金属原子和配体的大小，结构从聚合变为离散。根据这些结果，我们计划开发具有桥接配体的过渡金属团簇配合物，其中金属-金属键与配体pi系统之间的共轭作用更加增强。这类配合物的晶体有望表现出有趣的固态性质。

The purpose of this project was to develop understanding of intermolecular interactions and multipoint interactions which control the crystal structure of organometallic and organic crystals and also to prepare related new compounds. The results are summarized as follows : 1. A new type of electronically conjugated system with a new streric configuration was developed by utilizing metal-metal bond and organic pi systems. An example is dirhodium cluster complexes with 4 bridging aromatic ligands. The crystal structure of their cationic radical salts showed the formation of 3-dimensional interaction networks. 2. In inclusion complexes of cholic acid and their derivatives, host molecules are shown to dynamically recognize the quest molecules with conformational change of the functional groups of the host. 3. New derivatives of thio-, seleno- and teluro-carboxylic acids have been synthesized and some of their crystal structures were analyzed. 4. Syntheses of silanes and stannanes catalyzed by Group 10 homogeneous catalysts have been developed and structure of some of model complexes for the catalytic intermediates have been analyzed. 5. Liquid crystalline phase of organophosphazenes has been analyzed. 6. New supramolecules formed from Group 10 and 11 complexes have been prepared and their x-ray structures have been analyzed. The structure changes from polymeric to discrete depending on the metal atoms and the size of the ligands.As development from these results, we plan to develop a transition metal cluster complexes with bridging ligands with pi systems, in which the conjugation between metal-metal bond and ligand pi systems are more enhanced. Crystals of such type of complexes are expected to show interesting solid state properties.