Melinda Sindoro

Colloidal-Sized Metal–Organic Frameworks: Synthesis and Applications

Colloidal metal-organic frameworks (CMOFs), nanoporous colloidal-sized crystals that are uniform in both size and polyhedral shape, are crystals composed of metal ions and organic bridging ligands, which can be used as building blocks for self-assembly in organic and aqueous liquids. They stand in contrast to conventional metal-organic frameworks (MOFs), which scientists normally study in the form of bulk crystalline powders. However, powder MOFs generally have random crystal size and shape and therefore do not possess either a definite mutual arrangement with adjacent particles or uniformity. CMOFs do have this quality, which can be important in vital uptake and release kinetics. In this Account, we present the diverse methods of synthesis, pore chemistry control, surface modification, and assembly techniques of CMOFs. In addition, we survey recent achievements and future applications in this emerging field. There is potential for a paradigm shift, away from using just bulk crystalline powders, towards using particles whose size and shape are regulated. The concept of colloidal MOFs takes into account that nanoporous MOFs, conventionally prepared in the form of bulk crystalline powders with random crystal size, shape, and orientation, may also form colloidal-sized objects with uniform size and morphology. Furthermore, the traditional MOF functions that depend on porosity present additional control over those MOF functions that depend on pore interactions. They also can enable controlled spatial arrangements between neighboring particles. To begin, we discuss progress regarding synthesis of MOF nano- and microcrystals whose crystal size and shape are well regulated. Next, we review the methods to modify the surfaces with dye molecules and polymers. Dyes are useful when seeking to observe nonluminescent CMOFs in situ by optical microscopy, while polymers are useful to tune their interparticle interactions. Third, we discuss criteria to assess the stability of CMOFs for various applications. In another section of this Account, we give examples of supracrystal assembly in liquid, on substrates, at interfaces, and under external electric fields. We end this Account with discussion of possible future developments, both conceptual and technological.

Electric Field-Induced Assembly of Monodisperse Polyhedral Metal–Organic Framework Crystals

Monodisperse polyhedral metal-organic framework (MOF) particles up to 5 μm in size, large enough to enable in situ optical imaging of particle orientation, were synthesized by the strategy of simultaneous addition of two capping ligands with different binding strength during crystallization. Upon dispersing them in ethylene glycol and applying AC electric field, the particles facets link to form linear chains. We observe well-regulated crystal orientation not only for rhombic dodecahedra all of whose facets are equivalent, but also for truncated cubes with nondegenerate facets. After removing the electric field, chains disassemble if their facets contain even modest curvature, but remain intact if their facets are planar. This assembly strategy offers a general route to fabricate oriented polyhedral crystal arrays of potential interest for new applications and functions.

Near-Incompressible Faceted Polymer Microcapsules from Metal-Organic Framework Templates

Faceted polymer microcapsules are prepared from metal-organic framework (MOF) templates. The MOF templates are removable under mild aqueous conditions. The obtained microcapsules are stiffer than their spherical counterparts, reflecting the near-incompressibility of the facet edges, and indicating that the faceting might be a useful strategy for controlling the mechanical properties of polymer microcapsules.

Preorganized Chromophores Facilitate Triplet Energy Migration, Annihilation and Upconverted Singlet Energy Collection

Photon upconversion (UC) based on triplet-triplet annihilation (TTA) has the potential to enhance significantly photovoltaic and photocatalytic efficiencies by harnessing sub-bandgap photons, but the progress of this field is held back by the chemistry problem of how to preorganize multiple chromophores for efficient UC under weak solar irradiance. Recently, the first maximization of UC quantum yield at solar irradiance was achieved using fast triplet energy migration (TEM) in metal-organic frameworks (MOFs) with ordered acceptor arrays, but at the same time, a trade-off between fast TEM and high fluorescence efficiency was also found. Here, we provide a solution for this trade-off issue by developing a new strategy, triplet energy migration, annihilation and upconverted singlet energy collection (TEM-UPCON). The porous structure of acceptor-based MOF crystals allows triplet donor molecules to be accommodated without aggregation. The surface of donor-doped MOF nanocrystals is modified with highly fluorescent energy collectors through coordination bond formation. Thanks to the higher fluorescence quantum yield of surface-bound collectors than parent MOFs, the implementation of the energy collector greatly improves the total UC quantum yield. The UC quantum yield maximization behavior at ultralow excitation intensity was retained because the TTA events take place only in the MOF acceptors. The TEM-UPCON concept may be generalized to collectors with various functions and would lead to quantitative harvesting of upconverted energy, which is difficult to achieve in common molecular diffusion-based systems.

Voids and yolk-shells from crystals that coat particles.

We investigate curvature-driven core-shell morphology that emerges when polycrystalline shells of ZIF-8 (zeolitic imidazolate framework coordination polymer) grow on colloid-sized particles. In early growth stages, the shell is continuous, but it transforms to yolk-shell, with neither sacrificial template nor core etching, because of geometrical frustration. A design rule is developed regarding how local surface curvature matters. Comparing shells grown on cubic, rod-like, and peanut-shaped hematite core particles, we validate the argument.

Retraction of “Preorganized Chromophores Facilitate Triplet Energy Migration, Annihilation and Upconverted Singlet Energy Collection”

T authors retract this article because of scientific misconduct on the part of the first author, who was affiliated with Kyushu University at the time of the article’s publication. After the coauthors identified discrepancies in the raw data, the first author acknowledged his misconduct. An investigative panel at Kyushu University verified the scientific misconduct by the first author and also concluded that no other coauthors were engaged in the misconduct. The authors are unable to reproduce the fluorescence quantum yields of metal−organic framework (MOF) nanocrystals in the absence and presence of energy collector molecules (page 6546 left column, page 6547 left column). The solid-state upconversion emission spectra have not been confirmed at low excitation intensity as reported in Figure 3 and Figure 5. Also, the high stability under continuous laser excitation is not confirmed (Figure 3 and Figure 5). The authors deeply regret these circumstances and apologize to the scientific community for not having detected this research misconduct before publication. The original article was published on May 10, 2016, and retracted on June 8, 2017. Retraction