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一种烈性毒物，但它是基本的化学构件，也是大量无毒材料的重要组成部分。例如，含氰化物材料通常用于一次性手套、蓝色涂料，甚至用作食盐的防结块剂。用磷或砷原子取代氰化物(CN-)中的氮原子会产生氰化物的“重类似物”，即氰化物(Cp-)和氰苷(CPS-)。与氰化物一样，这些较重的类似物有可能在广泛的应用中得到利用。然而，目前还没有已知的方法来合成Cyapide或Cyarside离子，因此这些应用仍然是不可访问的。以前合成重氰化物类似物的尝试只是成功地将它们制成了不适合随后在材料化学中使用的非离子形式。该项目的目标是开发一种方法来生产作为离子盐的赛普赛德和赛普赛德。这些离子盐将比现有的含有氰化物和氰苷的化合物用途更广，并将允许探索重氰化物类似物的许多潜在应用。蓝色素和氰苷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)的磁性材料的组成部分。PBAs是由氰化物连接体连接的金属原子组成的材料，可以显示出有用的磁性，例如对热或光等刺激做出反应的能力。目前正在进行大量工作，以优化用于化学传感等技术的多溴联苯磺酸的磁性行为。限制当前研究努力的一个主要设计限制是，氰化物是唯一适合建造多溴联苯的离子。赛普赛德和赛尔赛德的离子盐将允许重氰化物类似物也用于多溴联苯，为其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合成离子氰化物和氰化钠盐的新方法，重氰酸盐类似物是一类新兴的化合物，有望成为重氰化物类似物的化学前体。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的离子盐合成的发展，下一个研究目标是使用它们来制造新型的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良好磁性的材料。

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.