Covalent Organic Frameworks: Pore Design and Interface Engineering.

Nature evolves fascinating molecular pores to achieve unique biological functions based on a single pore or channel as observed for aquaporins and ion channels. An artificial system, on the other hand, explores porous structures to construct dense pores in materials. Progress in chemistry over the past century has greatly improved our capability to synthesize porous materials. This is evident by the advancement from inorganic to organic units, from trial-and-error tests to module fabrication and further to fully predesignable pores, and from harsh preparation protocols to ambient synthetic methods. Over the past 15 years, a molecular platform based on organic and polymer chemistry has been explored to enable the design of artificial pores to achieve different pore size, shape, wall, and interface. This becomes possible with a class of emerging polymer-covalent organic frameworks (COFs). COFs are a class of crystalline porous polymers that integrate organic units into extended molecular frameworks with periodically ordered skeletons and well-defined pores. We have focused on exploring COFs over the past 15 years to design and synthesize porous structures with the aim of developing chemistry that leads to the creation of tailor-made pore interfaces (Nagai, A. et al. Nat. Commun., 2011, 2, 536). In this Account, we summarize the general concept of our approaches to various pore interfaces by emphasizing design principle, synthetic strategy, and distinct porous features and their impacts. We illustrate pore interface design by highlighting general strategies based on direct polymerization and pore surface engineering to construct different pore walls with a diversity of functional units. One distinct feature is that these functional groups are predesigned and synthetically controlled to achieve a predetermined component, position, and density, leading to a general way to install various specific pore wall interfaces to each pore. We showcase hierarchical pore interface architectures by elucidating the nature of interplays between interfaces and molecules and ions, ranging broadly from hydrogen bond to dipole-dipole/quadrupole interactions, electrostatic interaction, acid-base interaction, coordination, and electronic interactions. We scrutinize the unique properties and functions of adsorption and separation, catalysis, energy transformation and storage, and proton and metal ion transport by disclosing functional design schemes and interface-function correlations. We predict the fundamental key issues to be addressed and show future directions in designing artificial pores to target at ultimate functions. This chemistry on pore interface engineering opens a way to porous materials that have remained challenging in the predesign of both structure and function.