Organically templated polar metal oxyfluorides

固体化合物的一些物理性质与它们的晶体对称性有关。例如，在一个示例中，压电性和二次谐波产生（SHG）仅存在于非中心对称结构中（点群432也被排除在外）;热电性和铁电性需要在极性空间群类型中结晶。配位聚合物（MOFs）的多孔性和巨大的内表面使其具有许多有趣的性质和相关的潜在应用，如果它们能够在具有所需对称性约束的结构中结晶，则可以将其与上述电光或介电性质结合起来。拟议的项目旨在通过开发非中心对称金属有机固体的路线来应对这一挑战。通过引入极性氟氧化物基团[MOxFy]z-（M = V（V），Nb（V），Ta（V），Mo（VI），W（VI））作为金属配体，可以通过超分子合成对单个偶极取向进行定向控制并形成具有长程极性的结构。桥有机配体，主要是基于N-杂环，与功能基团的设计，以允许通过利用超分子相互作用，如氢键，π取向控制的极性积木…π堆积或阴离子π相互作用预期的结果包括产生新的SHG，压电和铁电材料与合并的极性无机单元作为一个原产地的散装极性，合成和（结构）表征的新的复杂的氟氧化物，开发tectons与超分子合成和新的路线制备新型金属有机配位化合物的功能组合。

Several physical properties of solid compounds correlate with their crystal symmetry. E.g., piezoelectricity and second harmonic generation (SHG) are present only in non-centrosymmetric structures (point group 432 is also excluded); pyro- and ferroelectricity require crystallization in a polar space group type. The interesting properties and related potential applications of coordination polymers (MOFs) which are based on their porosity and huge internal surface could be combined with the mentioned electrooptic or dielectric properties if they could be crystallized in structures with the required symmetry restraints. The proposed project is intended to tackle this challenge by development of routes to non-centrosymmetric metal-organic solids. By supramolecular synthesis directional control of individual dipole orientations and formation of structures with long-range polarity is anticipated by incorporation of polar oxyfluoride groups [MOxFy]z- (M = V(V), Nb(V), Ta(V), Mo(VI), W(VI)) as metalloligands. Bridging organic ligands, mainly based on N-heterocycles, with functional groups will be designed in order to allow orientational control of the polar building blocks by exploiting supramolecular interactions such as hydrogen bonds, pi...pi stacking or anion...pi interactions. Anticipated results include the generation of new SHG, piezoelectric and ferroelectric materials with incorporated polar inorganic units as an origin of bulk polarity, synthesis and (structural) characterization of new complex oxyfluorides, development of tectons with combined functionalities for supramolecular synthesis and new routes for the preparation of novel metal-organic coordination compounds.