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

无机化学、生物无机化学和金属有机化学项目的这一奖项支持罗格斯大学约翰·G·布伦南教授的研究，他的研究旨在合成、表征和相互转化含有稀土(Ln)金属和更重的硫族(E_2-、E_2-、Eph-；E=S、Se和Te)的分子、簇合物和固态化合物。一些新的配体体系将被使用，包括离子氟化物和更多的共价氢化物、氮化物和磷化物，以及一些日益复杂的杂配体和异金属体系。一个长期的目标是了解分子、团簇和固态Ln系统的化学键和物理性质之间的关系。这将通过研究稀土团簇的性质如何随团簇大小的变化来实现。第二个目标是了解日益复杂的集群系统的化学和物理属性，以便合理地设计具有所需属性的集群。配体的多样性为系统地平衡电荷、改变溶解度、控制空气敏感性以及影响簇合物中的Ln-Ln距离提供了机会。具有Ln-E键的分子和团簇显示出非凡的近红外发射特性，将这些化合物用作聚合物光纤的放大器是可行的。其中一些簇合物是将Ln掺杂到聚合物光纤中的理想候选者，因为它们具有固态Ln材料的特性(高Ln浓度、高量子效率)和分子化合物的特性(在有机溶剂中的溶解性、光学透明性)。还提出了一系列选择性的分子Ln(ER)3化合物。具有高度正电性的碲基阴离子的化合物被选择，因为它们将提供关于Ln-E键的性质的基本信息。氟化的R基团(即SeC6F5)被引入以形成可溶性和高发射性的分子。螯合配体(即2-Se-NC5H4)有望得到挥发性的Ln(ER)3化合物，在化学气相沉积过程中生成Ln2E3薄膜。所提出的分子和团簇是迄今为止报道的最有效的近红外发射类Ln化合物的成员，这对有机聚合物光纤的发展至关重要。研究生将接触到具有明确定义的工业应用的技术要求高的多学科研究经验，并将参与当地高中的化学活动。本科生在实验室里也一直很活跃，这些学生中的大多数继续攻读研究生或在当地行业工作。

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.