Symmetry-Guided Design of Advanced Porous Materials with Anticipated Porosities and Functionalities

For the past few decades, advanced porous materials (APMs) have attracted a tremendous amount of attention due to their fascinating structures and diverse applications. Metal-organic frameworks (MOFs), metal-organic polyhedra (MOPs) and porous polymer networks (PPNs) are important categories of APMs. By unravelling their structure-property relationships and employing the principles of group theory and topochemistry, this dissertation will focus on the rational design of these APMs with anticipated structures, porosities and properties. The vast majority of this dissertation will rely on the utilization of the tetrahedral building blocks in the construction of MOFs and PPNs. A few representative examples of MOMs with biomimetic features will also be presented. The first part of this dissertation introduces background knowledge for the chemistry of APMs. In addition to their definition and potential applications, it provides a systematic overview of different methods for the rational design of APMs. The second part illustrates the structures and gas storage applications of a series of MOFs constructed from a synthetically-accessible tetrahedral ligand. The study of symmetry-guided design of MOFs includes further exploration of tetrahedral ligands. The third part elucidates how the employment of topochemistry can lead to the discovery of a MOF with the largest porosity among all MOFs made from tetrahedral linkers. The symmetry-guided strategy can also be applied to the synthesis of PPNs. The fourth part describes the rational design, preparation and characterization of a commercially affordable PPN for highly efficient CO2 capture. Tetrahedral building units are also highly attractive for constructing mixed-ligand MOFs. In the next part is a close examination of the symmetry elements in Bravais lattices seen in MOFs, which has led to the discovery of a series of highly porous mixed-ligand MOFs. The sixth part discusses the design and synthesis two nucleobase-incorporated MOMs. It also briefly covers the rational design of MOMs with biomimetic features. In summary, a wide variety of APMs with anticipated structures and properties are rationally designed, based on a close examination of the symmetry elements of their basic building blocks. This work also offers a general perspective on the rational design of APMs with desired porosities and functionalities