Light Harvesting Antenna Properties of Framework Solids

CONSPECTUS: Energy transport within organic solids typically takes place via the movement of localized excitation or excitons, i.e., tightly bound electron-hole pairs. Exciton diffusion dynamics are crucial to applications like solar fuels production through photocatalysis and organic optoelectronics. Covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) are classes of framework solids that integrate ordered assemblies of chromophores. These materials possess properties desirable for the aforementioned applications. Their absorption cross sections across the ultraviolet-visible spectrum can be tuned via linker design. They are often crystalline and provide control over the framework topology in terms of spatial separation and relative orientation of chromophores. These properties allow for detailed understanding and tuning of structure- activity relationships. In this Account, we highlight our recent studies on photophysics and photonics of MOFs and COFs. Three materials are discussed with the focus on structural factors that govern the exciton properties in terms of diffusion, delocalization, and transport. The first is COF-5, a layered, two-dimensional COF with boronate ester linkages. We show that the molecular excitons in COF-5 are delocalized over multiple constituent building blocks with optical signatures of mixed (e.g., H-and J-type) excitonic interactions. The exciton of the S1 state decays and evolves into an excimer trap state in a few picoseconds. The excitons in COF-5 possess a diffusivity of about 0.02 cm2/s and a diffusion radius of about 5 nm based on exciton-exciton annihilation studies. To investigate the range of exciton diffusion, parallel exciton dynamics measurements were performed on COF-5 colloids with varying crystallite size, revealing that exciton diffusion is limited by crystallite size. The second system studied is an imine-linked two-dimensional COF with a hexagonal structure, the TAPB-DiOMe COF. To understand the photophysics of this material, we extended the study toward isomeric materials with a lower dimensionality: cofacially stacked nanotubes and free macrocycles assembled from the same primary building blocks. In-plane exciton delocalization and movement cannot occur in these lower dimensional species. We find that the exciton lifetime is prolonged significantly in the pi- stacked nanotubes where the macrocycles undergo planarization that restricts atomic movements of the imine bonds in the peripheral groups, which may reduce the rate of internal conversion. In addition, orientation-dependent anisotropic energy transfer through the nanotubes was detected via optical transient absorption anisotropy. The third system discussed is the MOF NDC-NU1000 decorated with single-atom metal-oxy (i.e., mix of oxo, hydroxo, and/or aqua) TiIV, CoIII, and NiII species mimicking single atom catalysts (SACs). These composite materials display photoinduced charge separation. We show the formation of charge separated states in these M-oxy decorated MOF samples upon photoexcitation with an electron transferred from the MOF linker to the M-oxy moiety. We compare and rationalize the differences in photoinduced charge separation kinetics among these M-oxy decorated MOFs and hope to identify energetic and structural factors that make the material an effective light harvesting platform and facilitate formation of the charge-separated state. Finally, we review our progress in context of the research published previously in the field and provide our perspective on the future of crystalline porous assemblies serving as light-harvesting antennae.