Over recent years, there has been a growing interest in utilizing two-dimensional conjugated porous organic polymers (2D-C-POPs) for a variety of applications including robust sensing, membrane separation, and controlled drug delivery. 2D-C-POPs are composed of carbon-rich aromatic skeletons and can be predesigned using a modular templated synthesis approach to promote polymerization in 2D. The most widely reported strategy to tailor the skeletal structures of 2D-C-POPs, involves the selection and tuning of building blocks to control the pore size, linkage chemistry, π-electron conjugation, and heteroatom functionalities. The scope for 2D-C-POPs functional applications is limited by challenges associated with fabricating them into scalable and adaptable form factors. In this thesis, I have explored the hierarchical design, synthesis, and properties of amorphous and crystalline 2D-C-POP materials tailored for environmental and biomedical applications.

Anisotropic 2D-C-POP films were readily tuned with different heteroatoms functionalities and processed using a facile drop-cast approach which produced uniform free-standing amorphous films of adaptable surface areas and thicknesses. Even though the films lacked long-range order, they exhibited inherent microporosity, out-of-plane anisotropy and were found composed of disorderly stacked 2D polymeric sheets that could be easily exfoliated into atomic-thin layers. The films displayed high sensitivity and fast response in the robust colorimetric sensing of acids and could be adapted into different device architectures for real-time sensing applications. These imine-linked films were then compared to analogs assembled from fluorine enriched building blocks. The addition of fluorine promoted tailorable surface properties, enhanced order in sheet stacking, and related functional properties.

Covalent Organic Frameworks (COFs) have long-range order and offer high surface areas and uniform pores architectures that make them an attractive platform for controlled-drug release. In this work, the novel synthesis of drug COF aerogels using one-pot synthesis approach to yield crystalline gels in a matter of minutes is reported. The hierarchical pore structure of the aerogels offers higher drug loading potential and improved and more controlled drug adsorption and release.

Together these directions entail two orthogonal approaches of hierarchical design of conjugated porous organic polymer architectures for enhancing the adaptability of these rich structures and their excellent properties in diverse application platforms.