Defect Engineering in Metal-Organic Framework Nanocrystals: Implications for Mechanical Properties and Performance.

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.

Vibrational Modes and Terahertz Phenomena of the Large-Cage Zeolitic Imidazolate Framework-71.

The zeolitic imidazole framework ZIF-71 has the potential to outperform other well-studied metal-organic frameworks due to its intrinsic hydrophobicity and relatively large pore size. However, a detailed description of its complex physical phenomena and structural dynamics has been lacking thus far. Herein, we report the complete assignment of the vibrational modes of ZIF-71 using high-resolution inelastic neutron scattering measurements and synchrotron radiation infrared spectroscopy, corroborated by density functional theory (DFT) calculations. With its 816 atoms per unit cell, ZIF-71 is the largest system yet for which frequency calculations have been accomplished employing the CRYSTAL17 DFT code. We discover low-energy terahertz dynamics such as gate-opening and shearing modes that are central to the functions and stability of the ZIF-71 framework structure. Nanoscale analytical methods based on atomic force microscopy (near-field infrared spectroscopy and AFM nanoindentation) further unravel the local chemical and mechanical properties of ZIF-71 single crystals.

Facile and Fast Transformation of Nonluminescent to Highly Luminescent Metal-Organic Frameworks: Acetone Sensing for Diabetes Diagnosis and Lead Capture from Polluted Water.

Metal-organic frameworks (MOFs) stand as one of the most promising materials for the development of advanced technologies owing to their unique combination of properties. The conventional synthesis of MOFs involves a direct reaction of the organic linkers and metal salts; however, their postsynthetic modification is a sophisticated route to produce new materials or to confer novel properties that cannot be attained through the traditional methods. This work describes the postsynthetic MOF-to-MOF transformation of a nonluminescent MOF (Zn-based Oxford University-1 material [Zn-BDC, where BDC = 1,4-benzene dicarboxylate] (OX-1)) into a highly luminescent framework (Ag-based Oxford University-2 material [Ag-BDC] (OX-2)) by a simple immersion of the former in a silver salt solution. The conversion mechanism exploits the uncoordinated oxygen atoms of terephthalate linkers found in OX-1, instead of the unsaturated metal sites commonly employed, making the reaction much faster. The materials derived from the OX-1 to OX-2 transformation are highly luminescent and exhibit a selective response to acetone, turning them into a promising candidate for manufacturing fluorometric sensors for the diagnosis and monitoring of diabetes mellitus. Our methodology can be extended to other metals such as lead (Pb). The fabrication of a polymer mixed-matrix membrane containing OX-1 is used as a proof-of-concept for capturing Pb ions (as pollutants) from water. This research instigates the exploration of alternative methodologies to confer MOFs with special aptitudes for photochemical sensing or for environmental applications such as water purification.

Near-Field Infrared Nanospectroscopy Reveals Guest Confinement in Metal-Organic Framework Single Crystals.

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 realization of such applications, however, is the successful incorporation of a functional guest confined 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 also further provides a new methodology for nanoscale-resolved physical and chemical identification of wide-ranging framework materials and designer porous systems for advanced applications.

Elucidating the Drug Release from Metal-Organic Framework Nanocomposites via In Situ Synchrotron Microspectroscopy and Theoretical Modeling.

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.