Solid-State Reactions of Molecular Crystals

拟议研究的目标集中在设计、发现和表征新的固态反应。首先，将最初的一组目标分子扩大到包括具有末端双键的基团以及具有中性不饱和配体的阳离子金属络合物，这将(A)促进新工艺的发现，(B)有助于有效地选择那些可能产生立体规则产物的材料。结晶学研究，以及完整的产品表征，将加深对与每个工艺相关的几何和化学机理的理解。其次，当没有单晶时，将通过粉末衍射技术来确定结构。除了对新材料的研究外，现有固相聚合体系的粉末X射线结构测定，如丙烯酸钾，将为结构-反应性数据库提供重要的新信息。第三，对固相反应过程中观察到的扩散X射线散射的分析将提供关于在固相反应中间阶段观察到的无序的新信息。第四，从肉桂酸到金属络合物的一系列分子固体将被照射在相应生色团吸收带的低能“尾巴”中。这一研究途径有望生产二聚体、低聚物和聚合物的单晶。最后，新合成的乙酰二元酸金属盐有望在辐射剂量测定方面具有良好的应用前景。%固相反应为化学专一性和立体专一性的合成提供了难得的机会，从而产生了新的齐聚物和聚合物，而新材料在技术领域的新应用的发现，如剂量测定和固相多肽合成，被视为工业上的优先事项。

The objectives of the proposed research focus on the design, discovery and characterization of new solid-state reactions. First, expansion of an initial set of target molecules to include groups with terminal double bonds as well as cationic metal complexes with neutral unsaturated ligands will both (a) promote the discovery of new processes, and (b) aid in the efficient selection of those materials likely to produce stereoregular products. Crystallographic studies, as well as full product characterization, will develop understanding of the geometrical and chemical mechanism associated with each process. Second, when single crystals are not available, structures will be determined by powder diffraction techniques. In addition to studies of new materials, powder X-ray structure determination of extant solid-state polymerization systems, such as potassium acrylate, will provide significant new information for a structure-reactivity database. Third, analysis of the diffuse X-ray scattering observed during the course of a solid-state reaction will provide new information on the disorder observed to occur at intermediate stages of solid-state reactions. Fourth, a series of molecular solids ranging from cinnamic acids to metal complexes will be irradiated in the low-energy "tail" of the absorption band of the corresponding chromophore. This avenue of research promises to produce single crystals of dimers, oligomers and polymers. Finally, newly-synthesized metal salts of acetylenedicarboxylic acid promise to be excellent prospects for new applications involving radiation dosimetry.%%%Solid state reactions offer exceptional opportunities for chemospecific and stereo specific synthesis leading to the production of new oligomers and polymers, and the discovery of novel applications for new materials in technological areas such as dosimetry and solid phase peptide synthesis are viewed as high priorities in industry.