luminescent nanoparticles with a scalable guest loading has been fabricated and characterized. The successful encapsulation of the organic dye (fluorescein) is supported by both experimental evidence and theoretical simulations. The measured optical band gap is found to be comparable with the computed values of a hypothetical guest−host system. Isolated monomers and aggregate species of fluorescein confined in ZIF-8 nanocrystals have been systematically investigated through fluorescence lifetime spectroscopy. The quantum yield (QY) of the obtained solid-state materials is particularly high (QY ∼ 98%), especially when the concentration of the fluorescein guest is low. Combining a blue LED chip and a thin photoactive film of fluorescein@ZIF-8, we demonstrate a device with good optical tunability for multicolor and white light emissions. Additionally, we show that the fluorescein@ZIF-8 nanoparticles exhibit an improved photostability due to the shielding effect conferred by the nanoconfinement of the host framework, making them promising candidates for practical applications such as solidstate lighting, photonics, and optical communications.

The growth process of metal–organic framework (MOF) nanocrystals defines their properties and functions. However, defects may be prevalent during the crystallization of even seemingly perfect MOFs, such as zeolitic imidazolate framework-8 (ZIF-8), and yet direct probing of such structural defects has been challenging because of the lack of nanoscale techniques to locally examine individual nanocrystals. Here, we directly study local defects, such as missing linkers or metal vacancies, in ZIF-8 nano- and microcrystals with near-field IR nanospectroscopy combined with density functional theory calculations. We track the chemical changes during crystallization and show that structural defects like zinc cations that are bound to molecules of the reactant gradually disappear with ripening of the crystals, while dangling and missing linker defects prevail. The resulting defect-terminating groups or open-metal sites produce mechanical anisotropy and reduce the Young’s modulus, as measured via tip force microscopy with nanoscale resolution and supported by theoretical modeling. However, these structural defects also open the door for defect engineering to tune the performance of ZIF-8 by offering additional adsorption sites for targeted catalytic reactions, chemical sensing, or gas capture.

Metal-organic frameworks (MOFs) can provide exceptional porosity for molecular guest encapsulation useful for emergent applications in sensing, gas storage, drug delivery and optoelectronics. Central to the realisation of such applications however is the successful incorporation of the guest material within the host framework. Here we demonstrate, for the first time, the feasibility of scattering-type scanning near-field optical microscopy (s-SNOM) and nano-Fourier transform infrared (nanoFTIR) spectroscopy, in concert with density functional theory (DFT) calculations to reveal the vibrational characteristics of the Guest@MOF systems. Probing individual MOF crystals, we pinpoint the local molecular vibrations and thus, shed new light on the host-guest interactions at the nanoscale. Our strategy not only confirms the successful encapsulation of luminescent guest molecules in the porous host framework in single crystals, but further provides a new methodology for nanoscale-resolved physical and chemical identification of wide-ranging framework materials and designer porous systems for advanced applications.

Nanocomposites comprising metal-organic frameworks (MOFs) embedded in a polymeric matrix are promising carriers for drug delivery applications. While understanding the chemical and physical transformations of MOFs during the release of confined drug molecules is challenging, this is central to devising better ways for controlled release of therapeutic agents. Herein we demonstrate the efficacy of synchrotron microspectroscopy to track the in situ release of 5-fluorouracil (5-FU) anticancer drug molecules from a drug@MOF/polymer composite (5-FU@HKUST-1/polyurethane). Using experimental time-resolved infrared spectra jointly with newly developed density functional theory calculations, we reveal the detailed dynamics of vibrational motions underpinning the dissociation of 5-FU bound to the framework of HKUST-1 upon water exposure. We discover that HKUST-1 creates hydrophilic channels within the hydrophobic polyurethane matrix hence helping to tune drug release rate. The synergy between a hydrophilic MOF with a hydrophobic polymer can be harnessed to engineer a tunable nanocomposite that alleviates the unwanted burst effect commonly encountered in drug delivery.

No abstract