Thermally Stable Organic and Inorganic Alkalides and Electrides

热稳定的有机和无机碱化物和电子化合物

• 批准号: 9988881
• 负责人: James Dye
• 金额: $ 52.8万
• 依托单位: Michigan State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-04-15 至 2004-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9988881&HistoricalAwards=false
• 关键词: Thermally; Stable; Organic; Inorganic; Alkalides

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.

该项目旨在合成和表征含有碱金属阳离子与有机笼络合剂络合的晶体盐，以及作为抗衡离子的碱金属阴离子（碱金属离子）或捕获电子（电子离子）。 为了提高热稳定性，重点将放在合成和使用叔胺氮杂型络合剂，这是更耐还原比目前使用的环状和双环聚醚。 将合成具有适合于所选碱金属阳离子的空腔的穴状或金刚烷状分子。 当阳离子的包封速率足够快时，游离配位剂将与碱金属在溶剂如甲胺或二甲醚中一起使用，以在溶液中产生碱金属化物或碱金属化物。 加入极性较低的共溶剂如三甲胺或乙醚将允许引发结晶。 缓慢冷却饱和溶液或缓慢除去极性更大（且挥发性更强）的共溶剂将用于生长适合于通过X射线衍射进行结构测定的晶体。 表征方法和物理性质研究将包括化学分析、光学吸收和反射、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用碱金属和碱土金属进行测量容易得多。 在努力合成一类新的无机沸石，碱金属加合物的全硅沸石也将被制备和表征。 这类新的碱金属和碱土金属化合物在材料科学界具有重要的意义。 新型导电材料对推进固态材料科学领域（如分子电子学）的重要性在各个行业中受到相当大的重视。