Novel Molecules and Solids Derived from the Cyaphide Ion

在化学系化学合成项目的支持下，印第安纳大学的Jose M. Goicoechea教授将研究一类新的由氰化物双原子类似物衍生的分子和固体。氰化物在化学的许多领域都有发现，从生物酶辅因子到定制磁性材料和催化剂。氰化物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，较重的含磷离子和含砷离子，分别是氰铁离子和氰苷离子，它们的化学性质尚未得到探索，尽管它们为合成有趣的磁性材料提供了巨大的潜力。该提案将探索几种分子目标的合成，这些目标将提供对这些新化学构建块的电子结构和性质的见解。最终，这将证明它们在设计一个全新的分子家族和配位聚合物方面的应用是至关重要的，这些分子和配位聚合物目前在化学文献中是缺失的。学生研究训练（本科生、高中生和研究生）和学生指导是项目的重要组成部分，为项目创建面向公众的互联网教育资源也是重要组成部分。本提案的科学目标是开发含有cyaphide （CP）和cyarside （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方案将这些活性基团转移到金属中心。获得含有这些CP和CAs基团的有机和过渡金属配合物，可以将它们的分子结构和化学反应性与含有更常见氰化物官能团的类似配合物进行比较。该项目的实验部分将以计算化学为补充和指导。有了这些物质，研究小组将探索具有桥接CP/CAs基团的多金属化合物的合成，以了解这些离子如何用于增强低聚物、聚合物和最终二维和三维扩展固体中金属中心之间的磁通信。将开发的合成方案最终将允许获得与普鲁士蓝相关的新配位化合物家族，普鲁士蓝是一类固体，在许多技术相关领域都有应用，包括磁性，传感，催化和储能。在更长的时间尺度上，这些发现有望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研究人员。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值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.