Synthesis of Heavy Cyanide Analogues (CP- and CAs-) for the Design of Novel Prussian Blue Analogues

虽然氰化物是众所周知的剧毒，但它是一种基本的化学成分，也是大量无毒物质的重要组成部分。例如，含氰化物的材料通常用于一次性手套、蓝色油漆，甚至作为食盐的防结块剂。将氰化物中的氮原子（CN-）替换为磷原子或砷原子将产生氰化物的“重类似物”，即氰皮（CP-）和氰苷（CPs-）。与氰化物一样，这些较重的类似物具有广泛应用的潜力。然而，目前还没有已知的方法来合成cyaphide或cyarside离子，因此这些应用仍然无法实现。先前合成重氰化物类似物的尝试只成功地将它们制成非离子形式，不适合随后在材料化学中使用。本项目的目的是开发一种生产氰皮和氰苷离子盐的方法。这些离子盐将比现有的含氰苷和氰苷的化合物用途更广泛，并将允许探索重氰化物类似物的许多潜在应用。cyaphide和cyarside的一个特别令人兴奋的应用将是作为一类称为普鲁士蓝类似物（PBAs）的磁性材料的成分。PBAs是由氰化物连接剂连接的金属原子组成的材料，可以表现出有用的磁性，例如对热或光等刺激的反应能力。目前正在进行重大努力，以优化PBAs的磁性行为，以便在化学传感等技术中使用。限制当前研究工作的一个主要设计限制是氰化物是唯一适合构建PBAs的可用离子。cyaphide和cyarside的离子盐将允许重氰化物类似物也用于PBAs，为它们的开发开辟了许多可能性。本项目旨在探索从重氰酸盐类似物中合成离子氰皮和氰苷盐的新方法，重氰酸盐类似物是一种新兴的化合物家族，有望成为重氰酸类似物的化学前体。这项研究将使重氰化物类似物能够用于新兴技术的设计材料，并属于EPSRC的“制造未来”研究主题。随着重氰化物类似物离子盐合成的发展，下一个研究目标是用它们来制造新的PBAs或其他类似的磁性材料，并研究如何利用它们来设计具有有利磁性能的材料。

Although cyanide is most well known for being a potent poison, it is a fundamental chemical building block and an important component of a large number of non-toxic materials. For example, cyanide-containing materials are commonly used in disposable gloves, blue paints, and even as anti-caking agents for table salt. Replacing the nitrogen atom in cyanide (CN-) with a phosphorus or arsenic atom would result in cyanide's "heavy analogues", cyaphide (CP-) and cyarside (CPs-). Like cyanide, these heavier analogues have the potential to be utilized in a wide range of applications. However, there is currently no known way to synthesize either cyaphide or cyarside ions, so these applications remain unaccessible. Previous attempts to synthesize the heavy cyanide analogues have only been successful in making them in non-ionic forms that are unsuitable for subsequent use in materials chemistry. The goal of this project is to develop a method for producing cyaphide and cyarside as ionic salts. These ionic salts would be much more versatile than existing cyaphide and cyarside containing compounds, and would allow the many potential applications of heavy cyanide analogues to be explored. A particularly exciting application for cyaphide and cyarside would be as components in a class of magnetic materials called Prussian Blue Analogues (PBAs). PBAs are materials consisting of metal atoms connected by cyanide linkers, and can exhibit useful magnetic properties such as the ability to respond to stimuli like heat or light. Significant effort is currently being directed toward optimizing the magnetic behaviour of PBAs for use in technologies such as chemical sensing. A major design constraint that limits current research efforts is that cyanide is the only available ion that is suitable for constructing PBAs. Ionic salts of cyaphide and cyarside would allow heavy cyanide analogues to also be used in PBAs, opening up many possibilities for their development. This project aims to explore novel methods for synthesizing ionic cyaphide and cyarside salts from the heavy cyanate analogues, an emerging family of compounds that show promise as chemical precursors to the heavy cyanide analogues. This research would enable heavy cyanide analogues to be utilized in designer materials for emerging technologies, and falls within the EPSRC's "Manufacturing the Future" research theme. Following the development of a synthesis for ionic salts of the heavy cyanide analogues, the next research objective is to use them to make novel PBAs or other similar magnetic materials, and to investigate how they can be utilized to design materials with advantageous magnetic properties.