Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

This review is divided into three different parts. In the introduction, the current applications of metal‐organic frameworks (MOFs) are shown. Furthermore, the overall stability, a comparison of phosphonate MOFs with carboxylate MOFs, the structural richness of phosphonate MOFs with the challenge in synthesis and different linker geometries is discussed. In the second part, several phosphonate MOFs with Y‐shaped planar, X‐shaped planar, and X‐shaped tetrahedral linker systems are described. The final part discusses different structures of inorganic building units (IBUs) with different metal atoms and a comparison of the formed MOF structures

Phosphonate Metal–Organic Frameworks: A Novel Family of Semiconductors

Herein, the first semiconducting and magnetic phosphonate metal–organic framework (MOF), TUB75, is reported, which contains a 1D inorganic building unit composed of a zigzag chain of corner‐sharing copper dimers. The solid‐state UV–vis spectrum of TUB75 reveals the existence of a narrow bandgap of 1.4 eV, which agrees well with the density functional theory (DFT)‐calculated bandgap of 1.77 eV. Single‐crystal conductivity measurements for different orientations of the individual crystals yield a range of conductances from 10−3 to 103 S m−1 at room temperature, pointing to the directional nature of the electrical conductivity in TUB75. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors.TU Berlin, Open-Access-Mittel - 202

Selective Water Transport in an Alanine-Functionalized Metal–Organic Framework: A Computational Study

Applications of metal–organic frameworks (MOFs) functionalized with biomolecules have primarily focused on the use of these frameworks for bioimaging, catalysis, chiral separation, nanomotors, and drug delivery. However, their use in the design of artificial water channels (AWCs) has yet to be explored. In this work, we computationally explore the performance of a zwitterionic alanine-functionalized Ni-CPO-27 MOF as an AWC. Using density functional theory (DFT) calculations and equilibrium/nonequilibrium molecular dynamics (MD) simulations, the stability, water permeability, and ion selectivity of the proposed AWC are studied. The DFT calculations predict that zwitterionic alanine binds to the coordinatively unsaturated Ni sites almost twofold stronger compared to water. Using the quantum theory of atoms in molecules, it is also found that the zwitterionic alanine molecules are further stabilized through hydrogen bonding between their carboxylate (COO–) and amino (NH3+) groups. Nonequilibrium MD simulations show that the proposed AWC possesses a high osmotic water permeability of 2.2 ± 0.3 × 10–15 cm3/s/channel, which lies between that observed in aquaporin-0 and aquaporin-1 proteins, while completely excluding Na+ and Cl– ions from the channel. The free energies associated with the water and ion transport show that fast water transport may be attributed to the relatively low free energy barriers for water in the channel, whereas the ion exclusion is due to large free energy barriers that the ions cannot overcome even under 100 MPa of applied pressure. By using a crystalline material, the proposed design of an amino acid-functionalized MOF-based AWC represents a departure from previously developed AWCs, which rely on the self-assembly of curated molecules in lipid bilayers or polymer matrices and are susceptible to long-term stability issues

A cobalt arylphosphonate MOF – superior stability, sorption and magnetism

We report a novel metal-organic framework (MOF) based on a cobalt arylphosphonate, namely, [Co2(H4-MTPPA)]·3NMP·H2O (1·3NMP·H2O), which was prepared solvothermically from the tetrahedral linker tetraphenylmethane tetrakis-4-phosphonic acid (H8-MTPPA) and CoSO4·7H2O in N-methyl-2-pyrrolidone (NMP). Compound 1 has the highest porosity (BET surface area of 1034 m2 g−1) ever reported for a MOF based on an aryl phosphonic acid linker. The indigo blue crystals of 1·3NMP·H2O are composed of edge-shared eight-membered Co2P2O4 rings, and are thermally very stable up to 500 °C.TU Berlin, Open-Access-Mittel - 201

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal-Organic Frameworks

Herein, the design and synthesis of a highly photoluminescent and electrically conductive metal–organic framework [Zn{Cu-p-H6TPPA}]⋅2 [(CH3)2NH] (designated as GTUB3), which is constructed using the 5,10,15,20-tetrakis [p-phenylphosphonic acid] porphyrin (p-H8TPPA) organic linker, is reported. The bandgap of GTUB3 is measured to be 1.45 and 1.48 eV using diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy, respectively. The PL decay measurement yields a charge carrier lifetime of 40.6 ns. Impedance and DC measurements yield average electrical conductivities of 0.03 and 4 S m−1, respectively, making GTUB3 a rare example of an electrically conductive 3D metal–organic framework. Thermogravimetric analysis reveals that the organic components of GTUB3 are stable up to 400 °C. Finally, its specific surface area and pore volume are calculated to be 622 m2 g−1 and 0.43 cm3 g−1, respectively, using grand canonical Monte Carlo. Owing to its porosity and high electrical conductivity, GTUB3 may be used as a low-cost electrode material in next generation of supercapacitors, while its low bandgap and high photoluminescence make it a promising material for optoelectronic applications

Semiconductive microporous hydrogen-bonded organophosphonic acid frameworks

Herein, we report a semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20‐tetrakis[p‐phenylphosphonic acid] porphyrin (GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction. A narrow band gap of 1.56 eV was extracted from a UV-Vis spectrum of pure GTUB5 crystals, in excellent agreement with the 1.65 eV band gap obtained from DFT calculations. The same band gap was also measured for GTUB5 in DMSO. The proton conductivity of GTUB5 was measured to be 3.00 × 10−6 S cm−1 at 75 °C and 75% relative humidity. The surface area was estimated to be 422 m2 g−1 from grand canonical Monte Carlo simulations. XRD showed that GTUB5 is thermally stable under relative humidities of up to 90% at 90 °C. These findings pave the way for a new family of organic, microporous, and semiconducting materials with high surface areas and high thermal stabilities.DFG, 414044773, Open Access Publizieren 2019 - 2020 / Technische Universität Berli

A 3D Cu‐Naphthalene‐Phosphonate Metal–Organic Framework with Ultra‐High Electrical Conductivity

A conductive phosphonate metal–organic framework (MOF), [{Cu(H2O)}(2,6‐NDPA)0.5] (NDPA = naphthalenediphosphonic acid), which contains a 2D inorganic building unit (IBU) comprised of a continuous edge‐sharing sheet of copper phosphonate polyhedra is reported. The 2D IBUs are connected to each other via polyaromatic 2,6‐NDPA's, forming a 3D pillared‐layered MOF structure. This MOF, known as TUB40, has a narrow band gap of 1.42 eV, a record high average electrical conductance of 2 × 102 S m−1 at room temperature based on single‐crystal conductivity measurements, and an electrical conductance of 142 S m−1 based on a pellet measurement. Density functional theory (DFT) calculations reveal that the conductivity is due to an excitation from the highest occupied molecular orbital on the naphthalene‐building unit to the lowest unoccupied molecular orbital on the copper atoms. Temperature‐dependent magnetization measurements show that the copper atoms are antiferromagnetically coupled at very low temperatures, which is also confirmed by the DFT calculations. Due to its high conductance and thermal/chemical stability, TUB40 may prove useful as an electrode material in supercapacitors.TU Berlin, Open-Access-Mittel – 202

Cationic metal organic frameworks synthesized from cyclotetraphosphazene linkers with flexible tentacles

MOFs based on group 12 metals, namely, [Zn2(O3PyCP)Cl4] (Zn-O3PyCp), [Cd(O3PyCP)(NO3)2].H2O (Cd-O3PyCp), and [Hg(O3PyCP)Cl2] (Hg-O3PyCp), were synthesized using a novel flexible molecular building block, octakis(3-pyridyloxy)cyclotetraphosphazene (O3PyCP), and group 12 metal salts (ZnCl2, Cd(NO3)2.6H2O, HgCl2). The crystals of each of the cationic frameworks were structurally characterized by single crystal X-ray diffraction, elemental, FT-IR, and thermogravimetrical (TGA) analysis. Due to the flexibility of O3PyCP building block, we were able to observe three distinct cationic frameworks with group 12 metal ions. We performed the atomically detailed simulations to compute H2 adsorption isotherms of the resulting frameworks at a pressure range of 0–1 bar at 77 K. Zn-O3PyCp exhibits the highest H2 uptake capacity (58.42 cm3 STP/g)

Phosphonate Metal-Organic Frameworks: A Novel Family of Semiconductors

Herein is reported the first semiconducting and magnetic phosphonate metal-organic framework (MOF), TUB75, which contains a one-dimensional inorganic building unit composed of a zig-zag chain of corner-sharing copper dimers. The solid-state UV-Vis spectrum of TUB75 reveals the existence of a narrow band gap of 1.4 eV, which agrees well with the 1.77 eV one obtained from DFT calculations. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors. </p

Arylphosphonate-Tethered Porphyrins: Fluorescence Silencing Speaks a Metal Language in Living Enterocyte

We report the application of a highly versatile and engineerable novel sensor platform to monitor biologically significant and toxic metal ions in live human Caco-2 enterocytes. The extended conjugation between the fluorescent porphyrin core and metal ions via aromatic phenylphosphonic acid tethers generates a unique turn off and turn on fluorescence and, in addition, shifts in absorption and emission spectra for zinc, cobalt, cadmium and mercury. The reported fluorescent probes p-H8TPPA and m-H8TPPA can monitor a wide range of metal ion concentrations via fluorescence titration and also via fluorescence decay curves. Cu and Zn-induced turn off fluorescence can be differentially reversed by the addition of common chelators. Both p-H8TPPA and m-H8TPPA readily pass the mammalian cellular membrane due to their amphipathic character as confirmed by confocal microscopic imaging of living enterocytes.</p