Enhancing Dynamic Spectral Diffusion in Metal-Organic Frameworks through Defect Engineering.

The crystal packing of organic chromophores has a profound impact on their photophysical properties. Molecular crystal engineering is generally incapable of producing precisely spaced arrays of molecules for use in photovoltaics, light-emitting diodes, and sensors. A promising alternative strategy is the incorporation of chromophores into crystalline metal-organic frameworks (MOFs), leading to matrix coordination-induced emission (MCIE) upon confinement. However, it remains unclear how the precise arrangement of chromophores and defects dictates photophysical properties in these systems, limiting the rational design of well-defined photoluminescent materials. Herein, we report new, robust Zr-based MOFs constructed from the linker tetrakis(4-carboxyphenyl)ethylene (TCPE4-) that exhibit an unexpected structural transition in combination with a prominent shift from green to blue photoluminescence (PL) as a function of the amount of acid modulator (benzoic, formic, or acetic acid) used during synthesis. Time-resolved PL (TRPL) measurements provide full spectral information and reveal that the observed hypsochromic shift arises due to a higher concentration of linker substitution defects at higher modulator concentrations, leading to broader excitation transfer-induced spectral diffusion. Spectral diffusion of this type has not been reported in a MOF to date, and its observation provides structural information that is otherwise unobtainable using traditional crystallographic techniques. Our findings suggest that defects have a profound impact on the photophysical properties of MOFs and that their presence can be readily tuned to modify energy transfer processes within these materials.

Kinetic Trapping of Photoluminescent Frameworks During High-Concentration Synthesis of Non-Emissive Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes with potential utility in gas separations, drug delivery, sensing, and catalysis. Small variations in MOF synthesis conditions can lead to a range of accessible frameworks with divergent chemical or photophysical properties. New methods to controllably access phases with tailored properties would broaden the scope of MOFs that can be reliably prepared for specific applications. Herein, we demonstrate that simply increasing the reaction concentration during the solvothermal synthesis of M2(dobdc) (M = Mg, Mn, Ni; dobdc4- = 2,5-dioxido-1,4-benzenedicarboxylate) MOFs unexpectedly leads to trapping of a new framework termed CORN-MOF-1 (CORN = Cornell University) instead. In-depth spectroscopic, crystallographic, and computational studies support that CORN-MOF-1 has a similar structure to M2(dobdc) but with partially protonated linkers and charge-balancing or coordinated formate groups in the pores. The resultant variation in linker spacings causes CORN-MOF-1 (Mg) to be strongly photoluminescent in the solid state, whereas H4dobdc and Mg2(dobdc) are weakly emissive due to excimer formation. In-depth photophysical studies suggest that CORN-MOF-1 (Mg) is the first MOF based on the H2dobdc2- linker that likely does not emit via an excited state intramolecular proton transfer (ESIPT) pathway. In addition, CORN-MOF-1 variants can be converted into high-quality samples of the thermodynamic M2(dobdc) phases by heating in N,N-dimethylformamide (DMF). Overall, our findings support that high-concentration synthesis provides a straightforward method to identify new MOFs with properties distinct from known materials and to produce highly porous samples of MOFs, paving the way for the discovery and gram-scale synthesis of framework materials.

Nanoscale semiconductor/catalyst interfaces in photoelectrochemistry.

Semiconductor structures (for example, films, wires, particles) used in photoelectrochemical devices are often decorated with nanoparticles that catalyse fuel-forming reactions, including water oxidation, hydrogen evolution or carbon-dioxide reduction. For high performance, the catalyst nanoparticles must form charge-carrier-selective contacts with the underlying light-absorbing semiconductor, facilitating either hole or electron transfer while inhibiting collection of the opposite carrier. Despite the key role played by such selective contacts in photoelectrochemical energy conversion and storage, the underlying nanoscale interfaces are poorly understood because direct measurement of their properties is challenging, especially under operating conditions. Using an n-Si/Ni photoanode model system and potential-sensing atomic force microscopy, we measure interfacial electron-transfer processes and map the photovoltage generated during photoelectrochemical oxygen evolution at nanoscopic semiconductor/catalyst interfaces. We discover interfaces where the selectivity of low-Schottky-barrier n-Si/Ni contacts for holes is enhanced via a nanoscale size-dependent pinch-off effect produced when surrounding high-barrier regions develop during device operation. These results thus demonstrate (1) the ability to make nanoscale operando measurements of contact properties under practical photoelectrochemical conditions and (2) a design principle to control the flow of electrons and holes across semiconductor/catalyst junctions that is broadly relevant to different photoelectrochemical devices.