Solid-State Reactions of Molecular Crystals

拟议研究的目标集中在新的固态反应的设计，发现和表征。 首先，将初始靶分子组扩展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将（a）促进新方法的发现，和（B）有助于有效选择可能产生有规立构产物的那些材料。 晶体学研究，以及完整的产品表征，将发展与每个过程相关的几何和化学机制的理解。 第二，当无法获得单晶时，将通过粉末衍射技术确定结构。 除了新材料的研究，粉末X射线结构测定现存的固态聚合体系，如丙烯酸钾，将提供重要的新信息的结构反应性数据库。 第三，在固态反应的过程中观察到的扩散X射线散射的分析将提供新的信息观察到的无序发生在固态反应的中间阶段。 第四，从肉桂酸到金属络合物的一系列分子固体将在相应发色团的吸收带的低能“尾部”被照射。 这一研究途径有望产生二聚体、低聚体和聚合物的单晶。 最后，新合成的乙炔二羧酸金属盐有望在辐射剂量学方面有很好的应用前景。固态反应为化学特异性和立体特异性合成提供了极好的机会，从而产生新的低聚物和聚合物，并且在诸如剂量测定和固相肽合成的技术领域中发现新材料的新应用被视为工业上的高度优先事项。

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.