Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded “Superassembly” Enables Nanoscale Enlargement of a Metal–Organic Rhomboid via a Solid-State Photocycloaddition

2018 ◽  
Vol 140 (14) ◽  
pp. 4940-4944 ◽  
Author(s):  
Qianli Chu ◽  
Andrew J. E. Duncan ◽  
Giannis S. Papaefstathiou ◽  
Tamara D. Hamilton ◽  
Manza B. J. Atkinson ◽  
...  
Keyword(s):  
Solid State ◽  
Metal Organic ◽  
Hydrogen Bonded

Unprecedented three-dimensional hydrogen-bonded hex topological chiral lanthanide–organic frameworks built from an achiral ligand

2018 ◽  
Vol 74 (11) ◽  
pp. 1403-1412 ◽  
Author(s):  
Tao Qin ◽  
Zhe Feng ◽  
Jie Yang ◽  
Xuan Shen ◽  
Dunru Zhu
Keyword(s):  
Solid State ◽  
Three Dimensional ◽  
Water Molecules ◽  
Space Group ◽  
X Ray Crystallography ◽  
Circularly Polarized Luminescence ◽  
Metal Organic ◽  
First Time ◽  
Green Photoluminescence ◽  
Hydrogen Bonded

The design and preparation of chiral metal–organic frameworks (CMOFs) from achiral ligands are a big challenge. Using 3-nitro-4-(pyridin-4-yl)benzoic acid (HL) as a new linker, a total of eight chiral lanthanide–organic frameworks (LOFs), namely poly[diaquatris[μ2-3-nitro-4-(pyridin-4-yl)benzoato-κ2 O:O′]lanthanide(III)], L- and D-[Ln(C12H7N2O4)3(H2O)2] n [(1), Ln = Eu; (2), Ln = Gd; (3), Ln = Dy; (4), Ln = Tb], were hydrothermally synthesized without chiral reagents and determined by X-ray crystallography. Crystal structure analyses show that L-(1)–(4) crystallize in the hexagonal P65 space group and are isomorphous and isostructural, while the enantiomers D-(1)–(4) crystallize in the hexagonal P61 space group. All LnIII ions are octacoordinated by six carboxyl O atoms of six 3-nitro-4-(pyridin-4-yl)benzoate ligands and two water molecules in a dodecahedral geometry. A one-dimensional neutral helical [Ln2(CO2)3] n chain is observed in (1)–(4) as a chiral origin. These helical chains are further interconnected via directional hydrogen-bonding interactions between pyridyl groups and water molecules to construct a three-dimensional (3D) homochiral network with hex topology. The present CMOF structure is the first chiral 3D hydrogen-bonded hex-net and shows good water stability. Solid-state circular dichroism (CD) signals revealed that (1)–(4) crystallized through spontaneous resolution. Furthermore, (1) and (4) display a strong red and green photoluminescence at room temperature, respectively, but their intensities reduce to almost half at 200 °C. Notably, upon excitation under visible light (463 nm), a circularly polarized luminescence (CPL) of (1) in the solid state is observed for the first time, with a g lum value of 2.61 × 10−2.

High hydroxide conductivity in a chemically stable crystalline metal–organic framework containing a water-hydroxide supramolecular chain

2016 ◽  
Vol 52 (54) ◽  
pp. 8459-8462 ◽  
Author(s):  
Sanjog S. Nagarkar ◽  
Bihag Anothumakkool ◽  
Aamod V. Desai ◽  
Mandar M. Shirolkar ◽  
Sreekumar Kurungot ◽  
...  
Keyword(s):  
Solid State ◽  
Metal Organic Framework ◽  
Ion Conductivity ◽  
Metal Organic ◽  
Supramolecular Chain ◽  
Crystalline Metal ◽  
Formed Hydrogen ◽  
Organic Framework ◽  
Hydrogen Bonded

A rationally designed cationic MOF containing an in-situ formed hydrogen bonded water-hydroxide anionic supramolecular chain exhibiting solid state hydroxide (OH−) ion conductivity is reported.

scholarly journals A Cavity‐Tailored Metal‐Organic Cage Entraps Gases Selectively in Solution and the Amorphous Solid State

2021 ◽  
Author(s):  
Jun-Long Zhu ◽  
Dawei Zhang ◽  
Tanya Ronson ◽  
Wenjing Wang ◽  
Lin Xu ◽  
...  
Keyword(s):  
Solid State ◽  
Amorphous Solid ◽  
Metal Organic

scholarly journals HKUST-1@IL-Li Solid-state Electrolyte with 3D Ionic Channels and Enhanced Fast Li+ Transport for Lithium Metal Batteries at High Temperature

Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 736
Author(s):  
Man Li ◽  
Tao Chen ◽  
Seunghyun Song ◽  
Yang Li ◽  
Joonho Bae
Keyword(s):  
High Temperature ◽  
Solid State ◽  
Solid Electrolyte ◽  
Metal Organic Framework ◽  
Ionic Channels ◽  
Transference Numbers ◽  
Lithium Metal ◽  
Lithium Metal Batteries ◽  
Metal Organic ◽  
Organic Framework

The challenge of safety problems in lithium batteries caused by conventional electrolytes at high temperatures is addressed in this study. A novel solid electrolyte (HKUST-1@IL-Li) was fabricated by immobilizing ionic liquid ([EMIM][TFSI]) in the nanopores of a HKUST-1 metal–organic framework. 3D angstrom-level ionic channels of the metal–organic framework (MOF) host were used to restrict electrolyte anions and acted as “highways” for fast Li+ transport. In addition, lower interfacial resistance between HKUST-1@IL-Li and electrodes was achieved by a wetted contact through open tunnels at the atomic scale. Excellent high thermal stability up to 300 °C and electrochemical properties are observed, including ionic conductivities and Li+ transference numbers of 0.68 × 10-4 S·cm-1 and 0.46, respectively, at 25 °C, and 6.85 × 10-4 S·cm-1 and 0.68, respectively, at 100 °C. A stable Li metal plating/stripping process was observed at 100 °C, suggesting an effectively suppressed growth of Li dendrites. The as-fabricated LiFePO4/HKUST-1@IL-Li/Li solid-state battery exhibits remarkable performance at high temperature with an initial discharge capacity of 144 mAh g-1 at 0.5 C and a high capacity retention of 92% after 100 cycles. Thus, the solid electrolyte in this study demonstrates promising applicability in lithium metal batteries with high performance under extreme thermal environmental conditions.

Rational strategies for proton-conductive metal–organic frameworks

2021 ◽  
Author(s):  
Dae-Woon Lim ◽  
Hiroshi Kitagawa
Keyword(s):  
Solid State ◽  
Potential Application ◽  
High Performance ◽  
Metal Organic Frameworks ◽  
Metal Organic ◽  
Solid State Electrolytes

Since the transition of energy platforms, the proton-conductive metal–organic frameworks (MOFs) exhibiting high performance have been extensively investigated with rational strategies for their potential application in solid-state electrolytes.

Photoactive Zr and Ti Metal‐Organic‐Frameworks for solid‐state solar cells

ChemPhysChem ◽  
2021 ◽  
Author(s):  
Arianna Melillo ◽  
Rocio Garcia ◽  
Sergio Navalon ◽  
Pedro Atienzar ◽  
Belen Ferrer ◽  
...  
Keyword(s):  
Solar Cells ◽  
Solid State ◽  
Metal Organic Frameworks ◽  
Metal Organic

A MOF based on a lead(II) 2-oxido-6-methylpyridine-4-carboxylate network

2020 ◽  
Vol 75 (4) ◽  
pp. 365-369
Author(s):  
Long Tang ◽  
Yu Pei Fu ◽  
Na Cui ◽  
Ji Jiang Wang ◽  
Xiang Yang Hou ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Carboxylic Acid ◽  
Thermogravimetric Analysis ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Connected Node ◽  
Metal Organic ◽  
Solid State Fluorescence

AbstractA new metal-organic framework, [Pb(hmpcaH)2]n (1), has been hydrothermally synthesized from Pb(OAc)2 · 3H2O and 2-hydroxy-6-methylpyridine-4-carboxylic acid (hmpcaH2; 2), and characterized by IR spectroscopy, elemental and thermogravimetric analysis, and single-crystal X-ray diffraction. In complex 1, each hmpcaH− ligand represents a three-connected node to combine with the hexacoordinated Pb(II) ions, generating a 3D binodal (3,6)-connected ant network. The crystal structure of 2 was determined. The solid-state fluorescence properties of 1 and 2 were investigated.

scholarly journals Spectroscopic, X-ray Diffraction and Density Functional Theory Study of Intra- and Intermolecular Hydrogen Bonds in Ortho-(4-tolylsulfonamido)benzamides

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 926
Author(s):  
Malose J. Mphahlele ◽  
Eugene E. Onwu ◽  
Marole M. Maluleka
Keyword(s):  
Density Functional Theory ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Density Functional ◽  
Tetrahedral Geometry ◽  
Hindered Rotation ◽  
Hydrogen Bond Acceptor ◽  
Functional Theory ◽  
Vis Spectroscopy ◽  
Hydrogen Bonded

The conformations of the title compounds were determined in solution (NMR and UV-Vis spectroscopy) and in the solid state (FT-IR and XRD), complemented with density functional theory (DFT) in the gas phase. The nonequivalence of the amide protons of these compounds due to the hindered rotation of the C(O)–NH2 single bond resulted in two distinct resonances of different chemical shift values in the aromatic region of their 1H-NMR spectra. Intramolecular hydrogen bonding interactions between the carbonyl oxygen and the sulfonamide hydrogen atom were observed in the solution phase and solid state. XRD confirmed the ability of the amide moiety of this class of compounds to function as a hydrogen bond acceptor to form a six-membered hydrogen bonded ring and a donor simultaneously to form intermolecular hydrogen bonded complexes of the type N–H···O=S. The distorted tetrahedral geometry of the sulfur atom resulted in a deviation of the sulfonamide moiety from co-planarity of the anthranilamide scaffold, and this geometry enabled oxygen atoms to form hydrogen bonds in higher dimensions.

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