Exploration of nanoscale metal coordination polymer synthesis using self-assembled block copolymer motifs

金属配位聚合物(MCP)因其骨架结构和化学组成而具有丰富的功能。但它们在溶剂中的溶解性通常很差，因此一旦制备就不能加工。这一局限性阻碍了MCP的广泛应用。为了应对这一挑战并研究与纳米结构相关的性质，合成可加工的纳米MCP(NMCP)粒子变得很有吸引力，并有可能为MCP纳米技术提供更丰富的功能。不幸的是，我们对这一上升区域的了解还很初级，也没有合理的结构变化的技术可用。相比之下，传统的有机聚合物是可加工的，它们的制备已经达到了先进的水平，可以用于分子工程的一些技术。结构定义聚合物的一种类型是嵌段共聚物，其中化学上不同的聚合物链段共价键合在一个分子中。这类分子在嵌段选择性溶剂或油/水混合溶剂中进行自组装，分别形成胶束状聚集体或油滴。嵌段共聚物超分子化学的这一方面已经得到了深入的研究，并在尺寸、形状甚至结构方面对所得到的组装施加了很大的控制。因此，我们打算将这一在嵌段共聚自组装方面发展起来的知识应用于最近出现的纳米材料创新领域。普鲁士蓝因其制备方法简单、通用性强，可作为MCP模型系统使用。这项研究将包括明确定义的氰基铁酸盐金属聚合物的合成、自组装和金属配位聚合，以试图开发制备可加工的、结构定义的功能性PB纳米粒子的策略。最终，建议的研究将导致在嵌段共聚物和NMCP的边界上建立一个研究子域。随着这一领域的建立和探索，一种全新的可加工的聚合物多孔纳米材料有望成为能源、医疗保健和安全应用的高需求。

Metal coordination polymers (MCP) possess rich functions derived from their framework structures and chemical composition. But they usually have poor solubility in solvents and therefore can not be processed once prepared. This limitation is hindering the widespread applicability of MCP. To address this challenge and to study nanostructure related properties, synthesis of processible nanoscale MCP (NMCP) particles becomes attractive and have potential to deliver richer functionality to MCP nanotechnologies. Unfortunately, our knowledge on this rising area is rudimentary and there is no technique available for rational structure variation. In contrast, conventional organic polymers are processible and their preparation has reached an advanced level with a few techniques available for molecular engineering. One type of structure-defined polymers is block copolymer, in which chemically different polymer segments are covalently bonded in one molecules. This type of molecules undergoes self-assembly in a block selective solvent or oil/water mixed solvents, leading to the formation of micelle-like aggregates or oil droples, respectively. This aspect of block copolymer supramolecular chemistry has been intensively studied and exerts great control on the resulting assemblies in terms of their size, shape, and even architecture. We therefore intend to apply this developed knowledge in block copolymer self-assembly to the recently emerged area of NMCP for nanomaterial innovation. Prusian blue will be used as a MCP model system because of its simplicity and generality in preparation. The research will involve well-defined cyanoferrate metallo-polymer synthesis, self-assembly and metal coordination polymerization in an attempt to develop strategies for the preparation of processible, structure-defined functional PB nanoparticles. Ultimately, the proposed research will lead to the establishment of a research subfield at the boundary of block copolymer and NMCP. A brand new type of processible polymeric porous nanomaterials, which is highly demanded for energy, healthcare and security applications, can be expected from the establishment and exploration of this area.