Novel Molecules and Solids Derived from the Cyaphide Ion

在化学系化学合成计划的支持下，印第安纳大学的Jose M.Goicoechea教授将研究一类新的分子和固体，这些分子和固体来自氰化物的双原子类似物。氰化物存在于化学的许多领域，从生物酶辅因子到定制的磁性材料和催化剂。氰盐通常用于大宗化学合成、电镀、冶金、熏蒸剂和杀虫剂等应用。相比之下，较重的含磷和含砷离子--分别是氰皮离子和氰苷离子--的化学成分尚未被探索，尽管它们为合成有趣的磁性材料提供了巨大的潜力。这项提议将探索几个分子靶标的合成，这将使我们深入了解这些新的化学构件的电子结构和性质。最终，这将证明它们在设计一种全新的分子和配位聚合物家族中的使用至关重要，这些分子和配位聚合物目前在化学文献中还没有出现。学生研究培训(本科生、高中生和研究生)和学生指导是该项目的重要组成部分，为该项目创建一个面向公众的互联网教育资源也是重要的组成部分。该计划的科学目标是开发含有氰基(CP)和氰苷(CAS)配体的新型有机金属化合物，用于通过复分解和交叉偶联反应转移这些官能团。Goicoechea小组的概念验证研究表明，这些物种是可分离的，含有这些新离子的试剂可以使用简单的盐分解反应规程将这些反应基团转移到金属中心。获得具有这些CP和CaS基团的有机和过渡金属络合物将允许比较它们的分子结构和化学反应活性与含有更常见的氰化物(CN)官能团的类似络合物。该项目的实验部分将得到计算化学的补充和指导。有了这些物种，研究小组将探索合成具有桥联Cp/CaS基团的多金属化合物，以了解这些离子如何用于增强齐聚物、聚合物以及最终二维和三维扩展固体中金属中心之间的磁通讯。将开发的合成方案最终将允许获得与普鲁士蓝相关的一系列新的配位化合物，普鲁士蓝是一种固体，在许多技术相关领域都有应用，包括磁性、传感、催化和能量存储。在更长的时间尺度上，这样的发现预计将使广泛的研究人员受益，特别是那些在材料科学领域工作的人。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Jose M. Goicoechea of Indiana University will study a new class of molecules and solids derived from diatomic analogs of cyanide. Cyanide is found across many areas of chemistry, ranging from biological enzyme cofactors to custom-made magnetic materials and catalysts. Cyanide salts are routinely used in applications including bulk chemical synthesis, electroplating, metallurgy, and as fumigants and insecticides. By contrast, the chemistry of the heavier phosphorus- and arsenic-containing ions, the cyaphide and cyarside ions, respectively, is unexplored despite the enormous potential they offer for the synthesis of interesting magnetic materials. This proposal will explore the synthesis of several molecular targets that will offer insight into the electronic structure and properties of these new chemical building blocks. Ultimately, this will prove critical for their use in the design of an entirely new family of molecules and coordination polymers that are currently absent in the chemical literature. Student research training (undergraduates, high school and graduate students) and student mentoring are important components of the project, as is the creation of a public-facing internet educational resource for the project.The scientific goal of this proposal is to develop novel organometallic compounds containing cyaphide (CP) and cyarside (CAs) ligands for the transfer of these functional groups through metathesis and cross-coupling reactions. Proof-of-concept research by the Goicoechea group suggests that such species are isolable, and that reagents containing these new ions can be made to transfer these reactive groups to metal centers using simple salt-metathesis reaction protocols. Obtaining organic and transition metal complexes with these CP and CAs groups will allow for comparisons of their molecular structures and chemical reactivities with analogous complexes containing the more common cyanide (CN) functional group. The experimental components of the project will be complemented with and guided by computational chemistry. With these species in hand, the research team will explore the synthesis of multi-metallic compounds with bridging CP/CAs groups to understand how these ions can be used to enhance magnetic communication between metal centers in oligomeric, polymeric and ultimately two- and three-dimensional extended solids. The synthetic protocols that will be developed will ultimately allow access to a new family of coordination compounds related to Prussian blue, a class of solids that have applications in numerous technologically relevant areas, including magnetism, sensing, catalysis, and energy storage. On a longer time scale, such discoveries are expected to benefit a broad range of researchers, particularly those working in materials science.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.