Two ZnII-based MOFs constructed with biphenyl-2,2′,5,5′-tetracarboxylic acid and flexible N-donor ligands: syntheses, structures and properties

Two new Zn2+-based metal–organic frameworks (MOFs) based on biphenyl-2,2′,5,5′-tetracarboxylic acid, i.e. H4(o,m-bpta), and N-donor ligands, namely, poly[[(μ4-biphenyl-2,2′,5,5′-tetracarboxylato)bis{[1,3-phenylenebis(methylene)]bis(1H-imidazole)}dizinc(II)] dimethylformamide monosolvate dihydrate], {[Zn2(C16H6O8)(C14H14N4)2]·C3H7NO·2H2O} n or {[Zn2(o,m-bpta)(1,3-bimb)2]·C3H7NO·2H2O} n (1) {1,3-bimb = [1,3-phenylenebis(methylene)]bis(1H-imidazole)}, and poly[[(μ4-biphenyl-2,2′,5,5′-tetracarboxylato)bis{[1,4-phenylenebis(methylene)]bis(1H-imidazole)}dizinc(II)] monohydrate], {[Zn2(C16H6O8)(C14H14N4)2]·H2O} n or {[Zn2(o,m-bpta)(1,4-bimb)2]·H2O} n (2) {1,4-bimb = [1,4-phenylenebis(methylene)]bis(1H-imidazole)}, have been synthesized under solvothermal conditions. The complexes were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction and powder X-ray diffraction analysis. Structurally, the (o,m-bpta)4− ligands are fully deprotonated and combine with Zn2+ ions in μ4-coordination modes. Complex 1 is a (3,4)-connected porous network with honeycomb-like [Zn2(o,m-bpta)] n sheets formed by 4-connected (o,m-bpta)4− ligands. Complex 2 exhibits a (2,4)-connected network formed by 4-connected (o,m-bpta)4− ligands linking Zn2+ ions in left-handed helical chains. The cis-configured 1,3-bimb and 1,4-bimb ligands bridge Zn2+ ions to form multi-membered [Zn2(bimb)2] loops. Optically, the complexes show strong fluorescence and display larger red shifts compared to free H4(o,m-bpta). Complex 2 shows ferroelectric properties due to crystallizing in the C 2v polar point group.

Download Full-text

Two CoII coordination polymers of biphenyl-2,2′,5,5′-tetracarboxylic acid with flexible N-donor ligands: syntheses, structures and magnetic properties

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229619009136 ◽

2019 ◽

Vol 75 (8) ◽

pp. 1073-1083 ◽

Cited By ~ 1

Author(s):

Feng Su ◽

Cheng-Yong Zhou ◽

Lin-Tao Wu ◽

Xi Wu ◽

Jing Su ◽

...

Keyword(s):

Coordination Polymers ◽

Three Dimensional ◽

Donor Ligands ◽

Tetracarboxylic Acid ◽

X Ray Diffraction ◽

Magnetic Studies ◽

Orbital Contribution ◽

X Ray ◽

3D Network ◽

Methyl Benzene

Two CoII-based coordination polymers, namely poly[(μ4-biphenyl-2,2′,5,5′-tetracarboxylato){μ2-1,3-bis[(1H-imidazol-1-yl)methyl]benzene}dicobalt(II)], [Co2(C16H6O8)(C14H14N4)2] n or [Co2(o,m-bpta)(1,3-bimb)2] n (I), and poly[[aqua(μ4-biphenyl-2,2′,5,5′-tetracarboxylato){1,4-bis[(1H-imidazol-1-yl)methyl]benzene}dicobalt(II)] dihydrate], {[Co2(C16H6O8)(C14H14N4)2(H2O)2]·4H2O} n or {[Co2(o,m-bpta)(1,4-bimb)2(H2O)2]·4H2O} n (II), were synthesized from a mixture of biphenyl-2,2′,5,5′-tetracarboxylic acid, i.e. [H4(o,m-bpta)], CoCl2·6H2O and N-donor ligands under solvothermal conditions. The complexes were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction and powder X-ray diffraction analysis. The bridging (o,m-bpta)4− ligands combine with CoII ions in different μ4-coordination modes, leading to the formation of one-dimensional chains. The central CoII atoms display tetrahedral [CoN2O2] and octahedral [CoN2O4] geometries in I and II, respectively. The bis[(1H-imidazol-1-yl)methyl]benzene (bimb) ligands adopt trans or cis conformations to connect CoII ions, thus forming two three-dimensional (3D) networks. Complex I shows a (2,4)-connected 3D network with left- and right-handed helical chains constructed by (o,m-bpta)4− ligands. Complex II is a (4,4)-connected 3D novel network with ribbon-like chains formed by (o,m-bpta)4− linkers. Magnetic studies indicate an orbital contribution to the magnetic moment of I and II due to the longer Co...Co distances. An attempt has been made to fit the χM T results to the magnetic formulae for mononuclear CoII complexes, the fitting indicating the presence of weak antiferromagnetic interactions between the CoII ions.

Download Full-text

Three Mn(II) metal organic frameworks with the same chemical compositions, but different topological structures and properties

CrystEngComm ◽

10.1039/d1ce00064k ◽

2021 ◽

Author(s):

Li Tian ◽

Zhi Long Ma ◽

Mengchen Wang ◽

Jian Yun Shi

Keyword(s):

Coordination Polymers ◽

Terephthalic Acid ◽

Metal Organic Frameworks ◽

Solvothermal Reaction ◽

Chemical Compositions ◽

X Ray Diffraction ◽

X Ray ◽

Multidentate Ligand ◽

Structures And Properties ◽

Metal Organic

Solvothermal reaction of a novel multidentate ligand 2,5-bis-(1,2,4-triazol-1-yl)-terephthalic acid (H2TTPA), with MnCl2 afforded three structurally different coordination polymers with the similar formula [Mn(TTPA)•H2O]n (Mn-(1-3)). Single-crystal X-ray diffraction analyses show that...

Download Full-text

Three 3D Metal-Organic Frameworks Constructed from Keggin Polyanions and Multi-nuclear AgI Clusters: Assembly, Structures and Properties

Zeitschrift für Naturforschung B ◽

10.5560/znb.2013-3007 ◽

2013 ◽

Vol 68 (7) ◽

pp. 778-788 ◽

Cited By ~ 8

Author(s):

Xiu-Li Wang ◽

Na Li ◽

Ai-Xiang Tian ◽

Jun Ying ◽

Guo-Cheng Liu ◽

...

Keyword(s):

Ir Spectroscopy ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

Hydrothermal Conditions ◽

X Ray ◽

Structures And Properties ◽

Elemental Analyses ◽

Metal Organic ◽

New Compounds ◽

Inorganic Ligands

Three Keggin-based metal-organic frameworks (MOFs) containing multi-nuclear silver subunits, [Ag7(ptz)5(H2O)2][H2SiMo12O40] (1), [Ag8(ptz)5(H2O)2][AsW12O40] (2) and [Ag7(ptz)5(H2O)][HAsMo12O40] (3) (ptzH=5-(4-pyridyl)-tetrazole), have been synthesized under hydrothermal conditions by changing the inorganic polyanions. The new compounds have been characterized by elemental analyses, TG analyses, IR spectroscopy, and single-crystal X-ray diffraction. In compound 1, the multi-nuclear Ag5(ptz)5 subunits are interconnected to form chains, which are further linked by AgI cations to construct a 3D MOF with large channels. Pairs of SiMo12O404- polyanions reside in the channels as penta-dentate inorganic ligands. In 2, six AgI cations link five ptz- anions to construct a hexa-nuclear subunit [Ag6(ptz)5]+, which is interconnected to form chains. These chains are further linked by AgI cations to construct a 3D MOF, where AsW12O403- polyanions reside as hexa-dentate ligands. Compound 3exhibits a 3D MOF based on Ag5(ptz)5 subunits, in which the hexa-dentate AsMo12O403- polyanions are incorporated. The rigid tetrazole-based ligand ptz- plays an important role in the formation of the multi-nuclear subunits of the title compounds. The electrochemical properties of compound 1and the photocatalytic properties of compounds 1and 3have been investigated.

Download Full-text

3D semiconducting Co–MOFs based on 5-(hydroxymethyl)isophthalic acid and imidazole derivatives: syntheses and crystal structures

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229620004970 ◽

2020 ◽

Vol 76 (5) ◽

pp. 398-404

Author(s):

Zhong-Xuan Xu ◽

Chun-Yan Ou ◽

Chun-Xue Zhang

Keyword(s):

Metal Organic Frameworks ◽

Three Dimensional ◽

Isophthalic Acid ◽

Donor Ligands ◽

X Ray Diffraction ◽

Hydrothermal Conditions ◽

X Ray ◽

Vis Spectroscopy ◽

Structural Differences ◽

Metal Organic

Two three-dimensional cobalt-based metal–organic frameworks with 5-(hydroxymethyl)isophthalic acid (H2HIPA), namely poly[[μ2-1,4-bis(2-methyl-1H-imidazol-1-yl)benzene-κ2 N 3:N 3′][μ2-5-(hydroxymethyl)isophthalato-κ2 O 1:O 3]cobalt(II)], [Co(C9H6O5)(C14H14N4)] n (1), and poly[tris[μ2-1,4-bis(1H-imidazol-1-yl)benzene-κ2 N 3:N 3′]bis[μ3-5-(hydroxymethyl)isophthalato-κ2 O 1:O 3:O 5]dicobalt(II)], [Co2(C9H6O5)2(C12H10N4)3] n (2), were synthesized under similar hydrothermal conditions. Single-crystal X-ray diffraction analyses revealed that 5-(hydroxymethyl)isophthalate (HIPA2−) and 1,4-bis(2-methyl-1H-imidazol-1-yl)benzene (1,4-BMIB) are simple linkers connecting cobalt centres to build a fourfold interpenetration dia framework in complex 1. However, complex 2 is a pillared-layer framework with a (3,6)-connected network constructed by 1,4-bis(1H-imidazol-1-yl)benzene (1,4-DIB) linkers, 3-connected HIPA2− ligands and 6-connected CoII centres. The above significant structural differences can be ascribed to the introduction of the different auxiliary N-donor ligands. Moreover, UV–Vis spectroscopy and Mott–Schottky measurements confirmed that complexes 1 and 2 are typical n-type semiconductors.

Download Full-text

Two 3D ZnII Metal–Organic Frameworks with 3- and 8-Fold Interpenetration: Syntheses, Structures, Photodegradation, and Photoluminescent Properties

Australian Journal of Chemistry ◽

10.1071/ch16368 ◽

2017 ◽

Vol 70 (3) ◽

pp. 314 ◽

Cited By ~ 4

Author(s):

Chuan-Bin Fan ◽

Xiang-Min Meng ◽

Yu-Hua Fan ◽

Zi-Ao Zong ◽

Xiao-Yin Zhang ◽

...

Keyword(s):

Single Crystal ◽

Metal Organic Frameworks ◽

Xrd Analysis ◽

Donor Ligands ◽

Photoluminescence Properties ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic ◽

Solvothermal Conditions ◽

Single Crystal Xrd Analysis

Two novel coordination polymers, namely {[Zn(sbdc)(bmib)]·0.4H2O}n (1) and {[Zn(sbdc)(bibd)]·DMF}n (2) (H2sbdc = 4,4′-stilbenedicarboxylic, bmib = 1,4-bis(2-methylimidazol-1-yl)butane, bibd = 1,1′-(1,4-butanediyl)bis(imidazole), DMF = N,N-dimethylformamide), have been acquired under solvothermal conditions, and have been characterised by elemental analysis, infrared spectra, thermogravimetric analysis, and single-crystal X-ray diffraction (XRD). Single-crystal XRD analysis reveals that 1 shows eight-fold interpenetrating 3D frameworks with a four-connected (66) sqc6 topology and 2 displays four-connected three-fold interpenetrating 3D frameworks. The flexible N-donor ligands play an important role in the construction of the final topological structures for 1 and 2. Furthermore, 1 and 2 exhibit good photodegradation capability and photoluminescence properties.

Download Full-text

POM-based metal–organic compounds: Assembly, structures and properties

Main Group Chemistry ◽

10.3233/mgc-210080 ◽

2021 ◽

pp. 1-18

Author(s):

Jian Li ◽

Zhe Liu ◽

Yue-Yan Liu ◽

Jie Liu ◽

Yuan-Yuan Li ◽

...

Keyword(s):

Infrared Spectrum ◽

Organic Compounds ◽

Organic Dyes ◽

X Ray Diffraction ◽

Hydrothermal Conditions ◽

X Ray ◽

Organic Hybrid ◽

Hybrid Compounds ◽

Structures And Properties ◽

Metal Organic

Four POM-based inorganic-organic hybrid compounds, which are {[(Cu·L1’·H2O)·(α-Mo8O26)0.5]·H2O}n (1), {(Cu·L2’·H2O)·(α-Mo8O26)0.5}n (2), {[(Cu·L3’·H2O)·(β-Mo8O26)0.5]·5H2O}n (3), {(Cu·L4’·H2O)·(β-Mo8O26)}n (4)[L1’ = 1,5-bis (4-carboxylpyridine) pentane dibromide, L2’ = 1,7-bis (4-carboxylpyridine) heptane dibromide, L3’ = 1,2-bis [(4-carboxylpyridine) - N-methylene] benzene dibromide, L4’ = 1,4-bis [(4-carboxylpyridine) - N-methylene] benzene dibromide] have been successfully synthesized under hydrothermal conditions by tuning ligands. Compounds 1–4 were characterized by single crystal X-ray diffraction, infrared spectrum (IR), powder X-ray diffraction (PXRD), and thermogravimetric (TG). The transformation of ligands have a momentous effect on the [Mo8O26]4 - structures of this series. In addition, the adsorption and photocatalytic properties of organic dyes for compounds 1–4 have been investigated.

Download Full-text

Novel Ba2+ and Pb2+ metal–organic frameworks based on a semi-rigid tetracarboxylic acid: syntheses, structures, topologies and luminescence properties

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229621005143 ◽

2021 ◽

Vol 77 (6) ◽

Author(s):

Yanwen Sun ◽

Zhen Chen ◽

Xiaozhong Wang ◽

Lei Wang ◽

Xue Yang ◽

...

Keyword(s):

Self Assembly ◽

Metal Organic Frameworks ◽

Three Dimensional ◽

Luminescence Properties ◽

Tetracarboxylic Acid ◽

X Ray Diffraction ◽

X Ray ◽

Secondary Building Units ◽

Metal Organic ◽

The Rich

Multidentate carboxylate ligands have been widely used in the construction of metal–organic frameworks (MOFs) owing to the rich variety of their coordination modes, which can lead to crystalline products with interesting structures and properties. Two new main-group MOFs, namely, poly[[di-μ-aqua-diaqua(dimethylformamide)[μ7-5,5′-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dibarium(II)] trihydrate], {[Ba2(C23H20O8)(C3H7NO)(H2O)4]·3H2O} n or {[Ba2(BTMIPA)(DMF)(H2O)4]·3H2O} n (1), and poly[[diaqua[μ6-5,5′-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dilead(II)] 2.5-hydrate], {[Pb2(C23H20O8)(H2O)2]·2.5H2O} n or {[Pb2(BTMIPA)(H2O)2]·2.5H2O} n (2), were prepared by the self-assembly of metal salts with the semi-rigid tetracarboxylic acid ligand 5,5′-methylenebis(2,4,6-trimethylisophthalic acid) (H4BTMIPA). Both structures were characterized by elemental analysis (EA), single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy and thermogravimetric analysis (TGA). Complex 1 reveals a three-dimensional (3D) flu network formed via bridging tetranuclear secondary building units (SBUs) and complex 2 displays a 3D framework with an sqp topology based on one-dimensional metal chains. The BTMIPA4− ligands adopt a rare coordination mode in 2, although the ligands in both 1 and 2 are X-shaped. The luminescence properties of both complexes were investigated in the solid state.

Download Full-text

Transition Metal Coordination Polymers with Trans-1,4-Cyclohexanedicarboxylate: Acidity-Controlled Synthesis, Structures and Properties

Materials ◽

10.3390/ma13020486 ◽

2020 ◽

Vol 13 (2) ◽

pp. 486

Author(s):

Pavel A. Demakov ◽

Artem S. Bogomyakov ◽

Artem S. Urlukov ◽

Aleksandra Yu. Andreeva ◽

Denis G. Samsonenko ◽

...

Keyword(s):

Three Dimensional ◽

Antiferromagnetic Coupling ◽

Controlled Synthesis ◽

Ambient Conditions ◽

X Ray Diffraction ◽

One Dimensional ◽

X Ray ◽

Structures And Properties ◽

Metal Organic ◽

Metal Coordination Polymers

Five trans-1,4-cyclohexanedicarboxylate (chdc2−) metal–organic frameworks of transition metals were synthesized in aqueous systems. A careful control of pH, reaction temperature and solvent composition were shown to direct the crystallization of a particular compound. Isostructural [Co(H2O)4(chdc)]n (1) and [Fe(H2O)4(chdc)]n (2) consist of one-dimensional hydrogen-bonded chains. Compounds [Cd(H2O)(chdc)]n∙0.5nCH3CN (3), [Mn4(H2O)3(chdc)4]n (4) and [Mn2(Hchdc)2(chdc)]n (5) possess three-dimensional framework structures. The compounds 1, 4 and 5 were further characterized by magnetochemical analysis, which reveals paramagnetic nature of these compounds. A presence of antiferromagnetic exchange at low temperatures is observed for 5 while the antiferromagnetic coupling in 4 is rather strong, even at ambient conditions. The thermal decompositions of 1, 4 and 5 were investigated and the obtained metal oxide (cubic Co3O4 and MnO) samples were analyzed by X-ray diffraction and scanning electron microscopy.

Download Full-text

Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

10.26434/chemrxiv.13146278.v1 ◽

2020 ◽

Author(s):

Pia Vervoorts ◽

Stefan Burger ◽

Karina Hemmer ◽

Gregor Kieslich

Keyword(s):

High Pressure ◽

State Of The Art ◽

Energy Landscape ◽

Structural Flexibility ◽

Zeolitic Imidazolate Frameworks ◽

Stimuli Responsive ◽

X Ray Diffraction ◽

X Ray ◽

Open Questions ◽

Metal Organic

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to p = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at p = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).

Download Full-text