Solid State Coordination Chemistry of Hybrid Oxide Materials

Jon Zubieta博士，雪城大学化学系，由化学系无机、生物无机和有机金属项目资助，研究杂化氧化物材料的固态配位化学。该项目将专注于控制合成亚稳但持久的扩展氧化物结构，这些结构是通过使用有机成分作为结构导向构建块而形成的。研究的重点是广泛相关的氧化物固体类别：(i)以M/P/O （M=V或Mo）无机骨架为特征的材料和（ii）具有V/O或Mo/O无机骨架的相。在这两种情况下，二级金属配体配合物或亚基将作为电荷平衡和结构导向成分。该合成方法涉及多胺配体、“仲”金属阳离子和无机氧化物源在水热介质中的低温自组装。将确定所得材料的结构，并开发控制其结构-性能关系的方法。目前，合理合成二维或三维固体材料的方法几乎没有。这是一个问题，因为为了实现先进材料科学和纳米技术的目标，必须掌握扩展结构的合成，这些目标包括为催化、量子电子学、光学、光子学、化学选择传感和太阳能转换等创造材料。复杂无机氧化物在地圈和生物圈的出现表明，大自然可以为合成相的制备和氧化物微观结构的修饰提供有用的指导。因此，一种设计新型氧化物材料的有效方法是模仿大自然使用有机分子来修饰无机结构。该项目将使用选定的“分子构建块”，其中包括已知可以指导金属配合物结构的有机化合物，以开发一种“修补玩具”方法来制备新材料。除了研究的潜在基础和实际意义外，这些活动将广泛影响研究生，博士后助理和休假研究员的培训，促进合作项目，以及为不同水平的专业知识和兴趣开发课程，教程和演示文稿。

Dr. Jon Zubieta, Chemistry Department, Syracuse University, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for research into the solid state coordination chemistry of hybrid oxide materials. The project will focus on the controlled synthesis of metastable but persistent extended oxide structures that are formed through the use of organic components as structure-directing building blocks. The research focuses on broadly related classes of oxide solids: (i) materials characterized by M/P/O (M=V or Mo) inorganic skeletons and (ii) phases with V/O or Mo/O inorganic skeletons. In both cases secondary metal-ligand complexes or subunits will be incorporated as charge-balancing and structure-directing constituents. The synthetic approach involves low temperature self-assembly of polyamine ligands, "secondary" metal cations, and the inorganic oxide sources in hydrothermal media. The structures of the resulting materials will be determined and methods to control their structure-property relationships will be developed. Presently, methods for the rational synthesis of two or three dimensional solid state materials are nearly absent. This is a problem because the synthesis of extended structures must be mastered in order to realize the objectives of advanced materials science and nanotechnology, which include creating materials for catalysis, quantum electronics, optics, photonics, chemoselective sensing, and solar energy conversion among others. The occurrence of complex inorganic oxides in the geosphere and the biosphere suggests that Nature may provide useful guidelines for the preparation of synthetic phases and for the modification of oxide microstructures. Thus, a powerful approach to the design of novel oxide materials mimics Nature's use of organic molecules to modify inorganic architectures. This project will use selected "molecular building blocks," which include organic compounds known to direct the structure of metal complexes, to develop a "Tinker Toy" methodology for preparing new materials. In addition to the potential fundamental and practical implications of the research, the activities will impact broadly on the training of graduate students, postdoctoral associates and sabbatical fellows, in the promoting of collaborative programs, and in the development of course work, tutorials and presentations for various levels of expertise and interest.