Symmetry-Breaking Charge Transfer in Metal-Organic Frameworks.

High quantum-yield charge carrier generation from the initially prepared excitons defines a key step in the light-harvesting and conversion scheme. Photoinduced charge transfer in molecular electron donor-acceptor assemblies is driven by a sizable Δ, which compromises the potential of the generated carriers. Reminiscent of the special pair at the reaction center of the natural light-harvesting complex, symmetry-breaking charge transfer (SBCT) within a pair of identical struts of metal-organic framework (MOF) will facilitate the efficient generation of long-lived charge carriers with maximized potentials without incorporating any foreign redox species.

Framework-Topology-Controlled Singlet Fission in Metal-Organic Frameworks.

Singlet fission (SF) has been explored as a viable route to improve photovoltaic performance by producing more excitons. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron superexchange to generate triplet pairs. However, strongly coupled chromophores often form excimers that can serve as an SF intermediate or a low-energy trap site.

Triplet Generation Through Singlet Fission in Metal-Organic Framework: An Alternative Route to Inefficient Singlet-Triplet Intersystem Crossing.

High quantum yield triplets, populated by initially prepared excited singlets, are desired for various energy conversion schemes in solid working compositions like porous MOFs. However, a large disparity in the distribution of the excitonic center of mass, singlet-triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy-coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin-orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution-stable MOFs.

Metal-Carbodithioate-Based 3D Semiconducting Metal-Organic Framework: Porous Optoelectronic Material for Energy Conversion.

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate "(-CS)M" linkage chemistry, entailing augmented metal-linker electronic communication.

Decoupling Redox Hopping and Catalysis in Metal-Organic Frameworks -based Electrocatalytic CO Reduction.

Traditional MOF e-CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi-electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e-CRR systems, CoPc@NU-1000 and TPP(Co)@NU-1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU-1000 MOF.

Superradiance and Directional Exciton Migration in Metal-Organic Frameworks.

Crystalline metal-organic frameworks (MOFs) are promising synthetic analogues of photosynthetic light-harvesting complexes (LHCs). The precise assembly of linkers (organic chromophores) around the topology-defined pores offers the evolution of unique photophysical behaviors that are reminiscence of LHCs. These include MOF excited states with photoabsorbed energy that is spatially dispersed over multiple linkers defining the molecular excitons.

Photoinduced Charge Transfer with a Small Driving Force Facilitated by Exciplex-like Complex Formation in Metal-Organic Frameworks.

Photoinduced charge transfer (PCT) is a key step in the light-harvesting (LH) process producing the redox equivalents for energy conversion. However, like traditional macromolecular donor-acceptor assemblies, most MOF-derived LH systems are designed with a large Δ to drive PCT. To emulate the functionality of the reaction center of the natural LH complex that drives PCT within a pair of identical chromophores producing charge carriers with maximum potentials, we prepared two electronically diverse carboxy-terminated zinc porphyrins, BFBP(Zn)-COOH and TFP(Zn)-COOH, and installed them into the hexagonal pores of NU-1000 via solvent-assisted ligand incorporation (SALI), resulting in BFBP(Zn)@NU-1000 and TFP(Zn)@NU-1000 compositions.

Physical properties of porphyrin-based crystalline metal‒organic frameworks.

Metal‒organic frameworks (MOFs) are widely studied molecular assemblies that have demonstrated promise for a range of potential applications. Given the unique and well-established photophysical and electrochemical properties of porphyrins, porphyrin-based MOFs are emerging as promising candidates for energy harvesting and conversion applications. Here we discuss the physical properties of porphyrin-based MOFs, highlighting the evolution of various optical and electronic features as a function of their modular framework structures and compositional variations.

Anthracene-Triphenylamine-Based Platinum(II) Metallacages as Synthetic Light-Harvesting Assembly.

Two trigonal prismatic metallacages and bearing triphenylamine and anthracene moieties are designed and synthesized to fabricate artificial light-harvesting systems (LHSs). These two cages are prepared via the coordination-driven self-assembly of two anthracene-triphenylamine-based tripyridyl ligand , three dicarboxylates, and six 90° Pt(II) acceptors. The design of the anthracene-triphenylamine chromophore makes possible the tunable excited-state property (like the emissive transition energy and lifetime) as a function of the solvent polarity, temperature, and concentration.

The role of photoinduced charge transfer for photocatalysis, photoelectrocatalysis and luminescence sensing in metal-organic frameworks.

Metal-organic frameworks (MOFs) have emerged as promising porous optoelectronic compositions for energy conversion and sensing applications. The enormous structural possibilities, the large variety of photo- and redox-active building blocks along with several post-synthetic functionalization strategies make MOFs an ideal platform for photochemical and photoelectrochemical developments. Because MOFs assemble all the active building units in a dense fashion, the non-aggregated yet proximally positioned species ensure efficient photon absorption to drive photoinduced charge transfer (PCT) reactions for energy conversion and sensing.

Improving Energy Transfer within Metal-Organic Frameworks by Aligning Linker Transition Dipoles along the Framework Axis.

Crystalline metal-organic frameworks (MOFs) can assemble chromophoric molecules into a wide range of spatial arrangements, which are controlled by the MOF topology. Like natural light-harvesting complexes (LHCs), the precise arrangement modulates interchromophoric interactions, in turn determining excitonic behavior and migration dynamics. To unveil the key factors that control efficient exciton displacements within MOFs, we first developed linkers with low electronic symmetry (as defined by large transition dipoles) and then assembled them into MOFs.