Solid-State Reactions of Molecular Crystals

分子晶体的固态反应

• 批准号: 0089257
• 负责人: Bruce Foxman
• 金额: $ 33.74万
• 依托单位: Brandeis 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: 2000-11-01 至 2004-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0089257&HistoricalAwards=false
• 关键词: Solid; State; Reactions; Molecular; Crystals

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.

提出的研究目标集中在设计、发现和表征新的固态反应。首先，扩大一组初始目标分子，使其包括末端双键基团以及带有中性不饱和配体的阳离子金属配合物，这将(a)促进新工艺的发现，(b)有助于有效选择可能产生立体规则产品的材料。晶体学研究，以及完整的产品表征，将发展对每个过程相关的几何和化学机制的理解。其次，当没有单晶时，结构将通过粉末衍射技术来确定。除了对新材料的研究外，现有固态聚合体系（如丙烯酸钾）的粉末x射线结构测定将为结构-反应性数据库提供重要的新信息。第三，对固体反应过程中观察到的漫射x射线散射进行分析，将为固体反应中间阶段观察到的无序提供新的信息。第四，从肉桂酸到金属配合物的一系列分子固体将在相应发色团吸收带的低能“尾巴”处照射。这一研究途径有望产生二聚体、低聚物和聚合物的单晶。最后，新合成的乙炔二羧酸金属盐在辐射剂量学等新领域具有良好的应用前景。固体反应为化学特异性和立体特异性合成提供了特殊的机会，导致新的低聚物和聚合物的生产，并且在诸如剂量学和固相肽合成等技术领域发现新材料的新应用被视为工业的重中之重。