New Frontiers in Coordination Chemistry: Designing Coordination Polymer and Phthalocyanine Materials with Novel Properties

这个配位化学研究项目的目标是含金属分子的合成、性质和应用，重点是(a)作为先进材料的配位聚合物（CP）和(b)不寻常的金属酞菁（PcM）。这些研究的核心是需要了解如何通过选择金属和设计合适的构建块和配体来控制金属配合物和CP的结构、性质和反应性。因此，如何使用构建块来制备CPs的问题至关重要，这些构建块提供了材料所显示的化学性质，并随后自组装成所需的3-D排列。同样，PcM分子是化学惰性的，具有氧化还原活性，在工业中广泛使用的强烈颜色的化合物。然而，尽管它们具有有用的特性，许多金属的PcM配合物的合成和反应性仍然几乎未被探索，它们的有机金属化学几乎是未知的。******为了解决这些问题，本研究计划利用我们在控制3D结构方面的成熟专业知识来设计具有有用的气相变色，发光，双折射，高折射率，热膨胀，磁性和其他性能的CP材料。我们将瞄准有毒气体传感器，如NH3、H2S、甲醛、SO2和Cl2，这些气体对工业安全、农业、纸浆/造纸厂、能源生产商和溜冰场都很重要。中子传感器（在核工业中至关重要）、可调谐发光材料、用于光重聚焦、显微镜和倍频的光学元件以及非常各向异性的热材料也将被设计出来。将阐明具有非传统早期过渡金属和f嵌段金属的PcM配合物的合成方案和结构，通过分离环还原/氧化物种探索PcM的氧化还原活性，并利用这些配体开发有机金属化学，使我们最终能够将这些工业相关的PcM材料用于新的化学工艺。******总的来说，这项研究将产生对结构-性能关系的基本理解，这将导致未来材料的合理设计。我们的氨传感器专利和高双折射光学材料专利表明了我们研究方法的重要性和可行性。提议的PcM研究合并了两个不同的领域（pc和有机金属），增加了我们对这类重要分子的广泛理解。******这个跨学科的研究项目还通过将口头/书面交流培训、与行业和其他利益相关者的互动、管理和国际经验融入学生生活的核心，为学生提供一流的HQP培训，超越高水平的实验室技能和安全，从而培养出最高质量、全面发展、具有全球意识的科学家。

This coordination chemistry research program targets the synthesis, properties and applications of metal-containing molecules, focusing on (a) coordination polymers (CP) as advanced materials and (b) unusual metallophthalocyanines (PcM). At the heart of these studies is the need to understand how to control structure, properties and reactivity of metal complexes and CP via the choice of metals and the design of appropriate building blocks and ligands. Thus, the question of how to prepare CPs using building blocks that provide the chemical properties to be displayed by the material, and which subsequently self-assemble into the desired 3-D arrangement are critically important. Similarly, PcM molecules are chemically inert, redox-active, intensely coloured compounds used extensively in industry. However, despite their useful attributes, the synthesis and reactivity of PcM complexes for many metals remains nearly unexplored and their organometallic chemistry is virtually unknown.******To address these issues, this research program exploits our established expertise in controlling 3D structure to design CP materials with useful vapochromic, luminescent, birefringent, high-refractive index, thermal expansion, magnetic and other properties. We will target sensors for toxic gases such as NH3, H2S, formaldehyde, SO2 and Cl2, which are important for industrial safety, agriculture, pulp/paper mills, energy producers and ice-rinks. Neutron sensors (critical in the nuclear industry), tunable light-emitting materials, optical components for light refocusing, microscopy and frequency-doubling, and very anisotropic thermal materials will also be designed. Synthetic protocols and structures of PcM complexes with non-traditional early-transition and f-block metals will be elucidated, Pc redox-activity will be explored by isolating ring-reduced/oxidized species and organometallic chemistry will be developed with these ligands, allowing us to eventually utilize these industrially relevant PcM materials for new chemical processes.******Overall, this research will generate a fundamental understanding of structure-property relationships, which will lead to the rational design of future materials. Our patented ammonia sensor and patent for highly birefringent optical materials indicates the significance and viability of our research approach. The proposed PcM research merges two disparate fields (Pcs and organometallics), increasing our broad understanding of this important class of molecules. ******This interdisciplinary research program also imparts top-class HQP training beyond high-level laboratory skills and safety by also infusing oral/written communications training, interactions with industry and other stakeholders, management and international experience into the core of student life so as to mold the highest quality, well-rounded, globally-minded scientists.