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

这个无机、生物无机和有机金属化学项目的奖项支持南卡罗来纳大学的Daniel Reger教授合成基于聚（吡唑基）硼酸盐、多主题聚（吡唑基）甲烷和相关配体的具有高度组织分子和超分子结构的新型配位化合物的研究。这些配体被设计成将一个或多个金属离子以预定的结构排列结合在一起，用于制备复杂的分子和超分子结构，这些结构具有独特的电学、光物理和磁性能。配体旨在将两种配位不饱和金属靠近，从而导致双金属活化，将用于制备一系列具有线性M-X-M离子桥的不寻常结构排列的均双金属配合物（M =第一行金属；X = F-, H-, Cl-, O2-, N3-）。配体具有足够的灵活性，可以允许不同的MM距离，从而产生各种不同的磁性，穆斯堡尔（M = Fe）和电化学性质。用新制备的不对称配体制备并研究了含有两种不同发光基团的杂双金属配合物。这些含有不同类型的多色金属中心的新配合物应该表现出光物理性质，这些性质将受到预期的高度组织的超分子结构的影响。在一种不同寻常的多色分子变化中，将制备含有光活性1,8-萘酰亚胺合子的配体的金属配合物。该基团具有强大的方向控制的pi堆叠相互作用，主导其超分子结构，从而能够制备不寻常的金属有机框架，包括高阶柱状网络。新开发的三（吡唑基）硼酸盐配体将用于自旋交叉Fe(II)N6配合物领域的基础性进展，具有可切换结构域的配合物有可能开发为存储器件。新的配合物将被制备和研究，这些配合物的附著官能团能够将Fe(II)N6配合物组织成高度有序的阵列，强烈影响自旋交叉行为。聚（吡唑基）甲烷配体可以作为轮烷的轴，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互锁化合物。通过与温斯顿-塞勒姆州立大学肯·布朗教授的合作，来自理科学生中代表性不足群体的本科生将与南卡罗来纳州小组合作。该公司还与当地女子学院哥伦比亚学院（Columbia College）达成协议，使用南卡罗来纳大学（University of South Carolina）的核磁共振和质谱设备。

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.