Molecules, Clusters, and Solid State Compounds with Lanthanide-Chalcogen Bonds

具有镧系元素-硫属元素键的分子、簇和固态化合物

• 批准号: 0747165
• 负责人: John Brennan
• 金额: --
• 依托单位: Rutgers University New Brunswick
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-01-15 至 2013-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0747165&HistoricalAwards=false
• 关键词: Molecules; Clusters; Solid; State; Compounds

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor John G. Brennan at Rutgers University to synthesize, characterize, and interconvert molecules, clusters, and solid-state compounds containing lanthanide (Ln) metals and the heavier chalcogens (E2-, EE2-, EPh-; E = S, Se, and Te). A number of new ligand systems will be used, including the ionic fluorides and more covalent hydrides, nitrides, and phosphides, as well as some increasingly complicated heteroligand and heterometallic systems. A long-term goal is to understand the relationships between the chemical bonding and physical properties of molecular, cluster, and solid state Ln systems. This will be accomplished by studying how lanthanide cluster properties vary as a function of cluster size. A second goal is to understand the chemistry and physical properties of increasingly complicated cluster systems in order to rationally design clusters with desired properties. The variety of ligands affords the opportunity to systematically balance charge, vary solubility, control air sensitivity, and influence Ln- Ln distances in cluster frameworks. Molecules and clusters with Ln-E bonds exhibit extraordinary near infra-red emission characteristics with the feasibility of using these compounds as amplifiers in polymer based optical fibers. Some of the proposed clusters are ideal candidates for doping Ln into polymer-based optical fibers, because they have properties that are a blend of the characteristics of solid-state Ln materials (high Ln concentrations, high quantum efficiencies) and those of molecular compounds (solubility in organic solvents, optical transparency). A select series of molecular Ln(ER)3 compounds are also proposed. Compounds with highly electropositive tellurium based anions have been chosen because they will provide fundamental information regarding the nature of the Ln-E bond. Fluorinated R groups (i.e. SeC6F5) are introduced to form soluble and highly emissive molecules. Chelating ligands (i.e. 2-Se-NC5H4) are expected to give volatile Ln(ER)3 compounds that deliver Ln2E3 thin films in chemical vapor deposition processes. The proposed molecules and clusters are members of the most efficient class of near-IR emitting Ln compounds reported to date, which is vital to the development of organic-polymer based optical fibers. Graduate students will be exposed to a technically demanding, multidisciplinary research experience with clearly defined industrial applications and will be involved in chemistry events at local high schools. Undergraduates are also consistently active in the laboratory, and most of these students continue on to graduate school or jobs in local industries.

这个奖项在无机，生物无机和有机化学计划支持研究教授约翰G。Brennan在罗格斯大学的研究，合成、表征和相互转化含有镧系（Ln）金属和较重硫属元素（E2-、EE 2-、EPh-; E = S、Se和Te）的分子、簇和固态化合物。 许多新的配体系统将被使用，包括离子氟化物和更共价的氟化物，氮化物和磷化物，以及一些越来越复杂的杂配体和杂金属系统。长期目标是了解分子、团簇和固态Ln系统的化学键和物理性质之间的关系。这将通过研究镧系元素团簇的性质如何随团簇大小而变化来实现。第二个目标是了解日益复杂的簇系统的化学和物理性质，以便合理地设计具有所需性质的簇。配体的多样性提供了系统地平衡电荷、改变溶解度、控制空气敏感性和影响簇框架中的Ln-Ln距离的机会。 具有Ln-E键的分子和团簇显示出非凡的近红外发射特性，具有将这些化合物用作聚合物基光纤中的放大器的可行性。一些提出的簇是将Ln掺杂到聚合物基光纤中的理想候选者，因为它们具有固态Ln材料（高Ln浓度，高量子效率）和分子化合物（在有机溶剂中的溶解度，光学透明度）的特性的混合物。选择一系列的分子Ln（ER）3化合物也提出了建议。选择了具有高正电性碲基阴离子的化合物，因为它们将提供关于Ln-E键性质的基本信息。引入氟化R基团（即SeC 6 F5）以形成可溶性和高发射性分子。 螯合配体（即2-Se-NC 5 H4）被期望产生挥发性Ln（ER）3化合物，其在化学气相沉积工艺中递送Ln 2 E3薄膜。所提出的分子和簇是迄今为止报道的最有效的一类近红外发射Ln化合物的成员，这对有机聚合物基光纤的发展至关重要。 研究生将接触到一个技术要求高，多学科的研究经验与明确定义的工业应用，并将在当地高中参与化学活动。 本科生也一直活跃在实验室，这些学生中的大多数继续研究生院或在当地行业工作。