Thermally Stable Organic and Inorganic Alkalides and Electrides

本项目旨在合成和表征含有碱阳离子与有机笼型络合物和碱金属阴离子（碱化物）或捕获电子（电子）作为反离子的结晶盐。为了提高热稳定性，重点将放在叔胺氮杂型络合物的合成和使用上，它比目前使用的环和双环聚醚更耐还原。将合成具有适合于选定碱阳离子的空腔的隐晶体或金刚烷类分子。当阳离子包封速度足够快时，游离络合剂将与碱金属在甲胺或二甲醚等溶剂中一起使用，生成溶液中的碱化物或电化物。加入极性较小的助溶剂，如三甲胺或乙醚，将允许结晶开始。缓慢冷却饱和溶液或缓慢去除极性更强（挥发性更强）的共溶剂将用于生长适合x射线衍射测定结构的晶体。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。如果像我们预期的那样，这些化合物至少在室温下是热稳定的，那么这种测量将比现在使用碱化物和电化物容易得多。为了合成一类新的无机电子，还将制备全硅沸石的碱金属加合物并对其进行表征。这些新类别的碱化物和电化物化合物在材料科学界具有重要意义。新型导电材料对推进固态材料科学领域的重要性，如分子电子学，在各个行业都受到相当的重视。

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.