半夹心有机金属自组装化合物的制备及2+2光化学关环反应研究

In the past few decades, topochemical photodimerization for cyclobutane or even ladderane ring formation has attracted considerable interest. Organometallic half-sandwich complexes have been frequently used in organometallic synthesis and catalysis because of their outstanding effect on chemical and physical properties. Such complexes were also ideal precursor for [2+2] photodimerization. This project will design a series of bridging ligands bearing one or more carbon-carbon doublebonds. Then multi-nuclear organometallic self-assemblies such as.metallarectangles and cages will be constructed by utilizing these ligands and half-sandwich organometallic edges. The size and shape of multi-nuclear self-assemblies could be controlled by adjusting ligands, “metallaedges”, reaction conditions and guest molecules in order that the distance between face-to-face olefin bonds is below the limit of the ‘‘Schmidt Distance’’. Photochemical properties and reactions of them will be fully researched and it will help us to explore potential applications of these organometallic functional materials. This research will bring new ideas and application prospects of organometallic optical materials; based on it we will try to develop our independent intellectual property rights of new optical materials.

近期科学界发现分子骨架中双键可通过光化学反应二聚为环丁烷骨架、乃至多个环丁烷串联的梯烷结构并得到越来越多的关注。众所周知，由于其突出的物理、化学性质，有机金属半夹心化合物被广泛用于有机金属合成和催化过程，这些化合物也是诱导2+2光化学反应的理想前体。本项目将设计一系列含一个乃至多个烯烃双键的桥联配体，令其与半夹心有机金属边壁反应，制备相应的多核有机金属自组装结构。通过调节配体、边壁、反应条件乃至客体分子可以调控此类多核自组装化合物的尺寸和形状，并使结构中双键距离落到“施密特距离”以下。此类化合物的光化学性质和反应将被充分研究并探索它们作为光学功能材料的潜在应用。通过本项目研究，争取在有机金属光学材料制备及相关技术方面取得一些有自主知识产权的研究成果。

科学界发现分子骨架中双键可通过光化学反应二聚为环丁烷骨架、乃至多个环丁烷串联的梯烷结构并得到越来越多的关注。众所周知，由于其突出的物理、化学性质，有机金属半夹心化合物被广泛用于有机金属合成和催化过程，这些化合物也是诱导2+2光化学反应的理想前体。本项目基于铑、铱半夹心有机金属角和一系列螯合与桥联配体组装成了相应的有机金属配合物，并研究了这些配合物的光化学反应。本项目发现桥联吡啶配体的光化学关环可诱导碳硼烷配体特定硼-氢键活化（从常见的2,9-位活化转变为2,8-位活化）。本项目还合成出一系列分子矩形、分子笼、具有特定拓扑结构如双环和三环互锁的超分子，并发现控制铑铱有机金属边壁的长度即可调控组装产物的拓扑结构。这些有机金属配合物展现出一定的有机反应催化性能。