Manipulating Metal Complex Assembly (and Function) via Structure-Directing "Third-Generation" Scorpionate Ligands

通过结构导向的“第三代”蝎形配体操纵金属络合物的组装（和功能）

• 批准号: 0715559
• 负责人: Daniel Reger
• 金额: $ 38.7万
• 依托单位: University South Carolina Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-08-01 至 2011-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0715559&HistoricalAwards=false
• 关键词: Manipulating; Metal; Complex; Assembly; Function

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Daniel Reger at the University of South Carolina to synthesize new types of coordination compounds with highly organized molecular and supramolecular structures based on poly(pyrazolyl)borate, multitopic poly(pyrazolyl)methane and related ligands. These ligands, which are designed to bond one or more metal ions in a predetermined architectural arrangement are used to prepare complex molecular and supramolecular structures that show distinct electrical, photophysical, and magnetic properties. Ligands designed to bring two coordinatively unsaturated metals into proximity, so as to result in bimetallic activation, will be used to prepare a series of homobimetallic complexes containing an unusual structural arrangement of a linear M-X-M ion bridge (M = first row metal; X = F-, H-, Cl-, O2-, N3-). The ligands are flexible enough to allow variable MM distances so as to yield a variety of distinct magnetic, Mossbauer (M = Fe) and electrochemical properties. Heterobimetallic complexes that contain two different luminophores will be prepared and studied with newly prepared un-symmetrical ligands. These new complexes containing different types of multi-chromophoric metal centers should exhibit photophysical properties that will be influenced by the anticipated highly organized supramolecular structures. In an unusual variation of multi-chromophoric molecules, metal complexes containing ligands with the photoactive 1,8-naphthalimide synthon will be prepared. This group has a strong directionally controlled pi-stacking interaction that dominates its supramolecular structures leading to the ability to prepare unusual metalorganic frameworks, including higher-order pillared networks. Newly developed tris(pyrazolyl)borate ligands will be used to make fundamental advancements in the field of spin-crossover Fe(II)N6 complexes, complexes with switchable domains with possibilities for development as memory devices. New complexes will be prepared and studied that have attached functional groups capable of organizing the Fe(II)N6 complexes into highly-ordered arrays, strongly impacting on the spin-crossover behavior. Poly(pyrazolyl)methane ligands will be developed that can act as the axle in rotaxanes, which can be functionalized with metal systems to prepare mechanically interlocked compounds containing photoactive metal units. Through a collaboration with Professor Ken Brown at Winston-Salem State University undergraduate students from underrepresented groups in science students will work with the South Carolina group. The also has an agreement with Columbia College, a local womens college, for the use of NMR and mass spectroscopy facilities at the University of South Carolina.

无机，生物无机和有机化学计划的这一奖项支持南卡罗来纳州大学的丹尼尔·雷格教授的研究，以合成基于聚（吡唑基）硼酸酯，多主题聚（吡唑基）甲烷和相关配体的具有高度组织的分子和超分子结构的新型配位化合物。这些配体被设计成以预定的结构布置键合一个或多个金属离子，用于制备显示出不同的电、光物理和磁性质的复杂分子和超分子结构。设计使两个配位不饱和金属接近以导致双金属活化的配体将用于制备一系列含有线性M-X-M离子桥（M =第一行金属; X = F-、H-、Cl-、O 2-、N 3-）的不寻常结构排列的同双金属配合物。 配体足够灵活，允许不同的MM距离，从而产生各种不同的磁性、穆斯堡尔谱（M = Fe）和电化学性质。将用新制备的不对称配体制备并研究含有两种不同发光体的异双金属配合物。这些新的配合物含有不同类型的多发色团金属中心，应表现出物理性质，将受到预期的高度组织的超分子结构。在多发色团分子的不寻常变化中，将制备含有配体的金属络合物与光活性1，8-萘二甲酰亚胺合成子。 该基团具有强的定向控制的π堆积相互作用，其主导其超分子结构，从而能够制备不寻常的金属有机框架，包括高阶柱撑网络。 新开发的三（吡唑基）硼酸盐配体将用于使自旋交叉Fe（II）N6配合物，具有可切换域的配合物作为存储器设备的发展的可能性领域的根本性的进步。 将制备和研究新的复合物，其具有能够将Fe（II）N6复合物组织成高度有序阵列的连接官能团，强烈影响自旋交叉行为。聚（吡唑基）甲烷配体将被开发，可以作为轴轮烷，它可以与金属系统功能化，以制备含有光活性金属单元的机械联锁化合物。通过与温斯顿-塞勒姆州立大学的肯·布朗教授的合作，来自理科学生代表性不足群体的本科生将与南卡罗来纳州小组合作。该研究所还与当地女子学院哥伦比亚学院达成协议，使用南卡罗来纳州大学的核磁共振和质谱设备。