具有开壳层电子结构的双核M-M金属多重键单元在构筑分子基材料领域有着重要的潜在应用前景。基于金属键单元外部配位场空间结构对称性和单元内部微观电子结构类型这一对立统一的内在关联效应，本项目拟提出采用碱解经典型dsp2杂化轨道金属键化合物反应生成新型d2sp3杂化轨道金属键化合物的途径，并结合结构对称性调控影响金属键键型转化的设计思想，通过空间结构设计实现金属键微观电子结构的有效调控。研究内容包括：通过控制金属键中心桥接氧原子数目和轴向配体性质调控金属键电子结构转化；应用多氧酸根电中和及螯合熵效应提高高氧化态金属多重键的稳定性；通过磁性、电子光谱和电化学测试，并结合理论计算研究此类开壳层金属多重键的反应性及成键机理。通过本项目的研究，获得更多新型金属键类型、键型转化以及空间结构对称性影响金属键微观电子结构等相关规律，补充完善金属键理论，丰富现代结构无机化学。

The construction of molecular materials with the open electronic structure of metal-metal bonds dimer has been of growing interest owing to their potential applications. Based on the relational effect between the external coordination symmetry environment of metal multiple bonds and the internal electronic configuration, this project will utilize base reaction with classical dsp2 hybridized orbital metal-metal bonds compounds to produce the novel d2sp3 hybridized orbital metal-metal bonds compounds. Combined with the structural symmetry of the control effect on metal bonds type conversion, the ligand field structure design is employed to tune the multiple metal bonds microstructure. Research work including: tuning the electronic structure through introducing different number of bridging oxygen atoms and variety axial ligands for the edge-sharing bioctahedral metal dimer; improving the stability of multiple bond with the high oxidation state by charge neutralization and chelating entropy increase effect of inorganic acid radical anions. The metal-metal bonding mechanism will be proposed based on the crystal structures, Uv-Vis, CV, magnetic properties and theoretical calculations. The purposes of the project are: (1) to get more rules about the new multiple metal bonds, its conversion and reaction properties; (2) to develop the metal-metal bonds theory and improve the modern inorganic structural chemistry.