Thermally Stable Organic and Inorganic Alkalides and Electrides

该项目旨在合成和表征结晶盐，其中含有由有机笼络合剂络合的碱金属阳离子以及作为抗衡离子的碱金属阴离子（碱金属）或捕获的电子（电子化合物）。 为了增强热稳定性，重点将放在叔胺氮杂型络合剂的合成和使用上，该络合剂比目前使用的环状和双环聚醚更耐还原。 将合成具有适合所选碱金属阳离子的空腔的类穴状配体或金刚烷类分子。 当阳离子的包封速率足够快时，游离络合剂将与碱金属在溶剂如甲胺或二甲醚中一起使用以在溶液中产生碱化物或电子化合物。 添加极性较小的共溶剂如三甲胺或乙醚将引发结晶。 饱和溶液的缓慢冷却或极性较大（且挥发性较大）的共溶剂的缓慢去除将用于生长适合通过 X 射线衍射确定结构的晶体。 表征方法和物理性质研究将包括化学分析、光学吸光度和反射率、磁化率、脉冲 EPR 和 ENDOR 以及核磁共振差示扫描量热法和电导率。 如果正如我们预期的那样，这些化合物至少在室温下具有热稳定性，那么这种测量将比现在使用碱化物和电子化合物进行的测量容易得多。 为了合成一类新型无机电子化合物，还将制备并表征全硅沸石的碱金属加合物。 这些新类别的碱化物和电子化合物在材料科学界具有重要意义。 新型导电材料对于推进固体材料科学领域（例如分子电子学）的重要性在各个行业中受到相当大的重视。

This project aims to synthesize and characterize crystalline salts that contain alkali cations complexed by organic cage complexants and either alkali metal anions (alkalides) or trapped electrons (electrides) as the counter-ions. In order to enhance thermal stability, the emphasis will be on the synthesis and use of tertiary amine aza-type complexants, which are more resistant to reduction than the currently used cyclic and bicyclic polyethers. Cryptand-like or adamanzane-like molecules with cavities appropriate for selected alkali cations will be synthesized. When the rate of encapsulation of the cation is fast enough, the free complexant will be used with the alkali metal in a solvent such as methylamine or dimethyl ether to produce the alkalide or electride in solution. Addition of a less polar co-solvent such as trimethylamine or diethyl ether will permit crystallization to be initiated. Slow cooling of the saturated solution or slow removal of the more polar (and more volatile) co-solvent will be used to grow crystals suitable for structure determination by X-ray diffraction. Characterization methods and physical property studies will include chemical anaylsis, optical absorbance and reflectance, magnetic susceptibility, pulsed EPR and ENDOR and nuclear magnetic resonance differential scanning calorimetry and conductivity. Such measurements will be much easier than are now possible with alkalides and electrides if, as we anticipate, the compounds are thermally stable to at least room temperature. In an effort to synthesize a new class of inorganic electrides, alkali metal adducts to all-silica zeolites will also be prepared and characterized. These new classes of alkalides and electride compounds are of great inferent in the materials sciences community. The importance of novel conducting materials to advancing areas of solid state materials sciences, such as molecular electronics, is receiving considerable emphasis in various industries.