Exploring Applications of Covalent Organic Frameworks: Homogeneous Reticulation of Radicals for Dynamic Nuclear Polarization.

Rapid progress has been witnessed in the past decade in the fields of covalent organic frameworks (COFs) and dynamic nuclear polarization (DNP). In this contribution, we bridge these two fields by constructing radical-embedded COFs as promising DNP agents. Via polarization transfer from unpaired electrons to nuclei, DNP realizes significant enhancement of NMR signal intensities. One of the crucial issues in DNP is to screen for suitable radicals to act as efficient polarizing agents, the basic criteria for which are homogeneous distribution and fixed orientation of unpaired electrons. We therefore envisioned that the crystalline and porous structures of COFs, if evenly embedded with radicals, may work as a new "crystalline sponge" for DNP experiments. As a proof of concept, we constructed a series of proxyl-radical-embedded COFs (denoted as PR( x)-COFs) and successfully applied them to achieve substantial DNP enhancement. Benefiting from the bottom-up and multivariate synthetic strategies, proxyl radicals have been covalently reticulated, homogeneously distributed, and rigidly embedded into the crystalline and mesoporous frameworks with adjustable concentration ( x%). Excellent performance of PR( x)-COFs has been observed for DNP 1H, 13C, and 15N solid-state NMR enhancements. This contribution not only realizes the direct construction of radical COFs from radical monomers, but also explores the new application of COFs as DNP polarizing agents. Given that many radical COFs can therefore be rationally designed and facilely constructed with well-defined composition, distribution, and pore size, we expect that our effort will pave the way for utilizing radical COFs as standard polarizing agents in DNP NMR experiments.