Multicomponent Approaches for the Generation of Structurally Diverse Microporous Coordination Polymers.

[摘要] Microporous coordination polymers (MCPs), materials built from metal clusters bridged with organic linkers, constitute a rapidly growing class of porous solids. The conventional synthetic strategies for production of MCPs involve coordination polymerization of one type linker with a single metal. Despite the success of this method, there exist several challenges with regard to producing highly porous and commercially viable MCPs. These disadvantages include interpenetration of frameworks upon linker extension causing a reduction in porosity and the requirement for synthetically complex linkers to achieve high porosity leading to a drastic increase in cost. This thesis is focused on multicomponent approaches for synthesis of structurally diverse MCPs. In addition, using multiple building units enables suppression of interpenetration, higher predictability over network topology, and an overall reduction in cost. Chapter 2 describes a coordination copolymerization approach of three carboxylate linkers; this strategy was employed to generate a series of isoreticular (having the same network topology) pillared-layer MCPs wherein structures were tuned uniaxially via controllable replacement of pillar linker. Moreover, pillar linker extension occurred in absence of interpenetration resulting in highly porous MCPs. The coordination terpolymerization strategy described in chapter 2 is also exploited to alter the connectivity within the layer arrangement of a pillared-layer MCP in chapter 3. Using a mixture of commercially available linkers of differing lengths enabled formation of a pillared-layer MCP with a non-regular layer structure and no interpenetration. In chapter 4 the power of the multicomponent approach is leveraged through covalent bond formation in tandem with coordination chemistry. A linker was designed which allows either coordination processes or a combination of coordination processes and covalent bond formation to occur in presence of Zn(II). Upon addition of various reaction partners, materials with variable architectures and pore characteristics are obtained. This approach, in addition to being a compelling material discovery method, also offers a fundamental understanding of factors influencing the two distinct modes of assembly.

[发布机构] University of Michigan

[效力级别] Chemistry

[关键词] Multicomponent Approaches for the Generation of Structurally Diverse Microporous Coordination Polymers;Chemistry;Science;Chemistry