Natural and synthetic metal oxalates – a topology approach

Dazem, Cyrielle L.F.; Noa, Francoise M. Amombo; Nenwa, Justin; Öhrström, Lars

doi:10.1039/c9ce01187k

Cited by 18 publications

(14 citation statements)

References 35 publications

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“…Though not described before, the laf-net can be found in the ToposPro 26 The laf-net has large rectangular channels running in two directions, and we speculate that larger cations, not fitting into the space in the kgd-nets, might template this network just as some larger cations induce the srs and other 3D-nets in the tris-oxalate-based systems. 24,25,27 The Concept of Foldable Nets. Inspecting the physical model in Figure 5, we noted that this net can be "folded" along the tetragonal axis while the individual hexagonal and trigonal geometries stay exactly the same; see Figure 7.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In terms of chirality, these versions of the kgd-net with trisbischelating octahedral metal centers share some features with the honeycomb (hcb) nets constructed from tris-oxalate coordination entities. 24,25 The latter contain alternating Δ or Λ enantiomers of the metal complexes, and in all examples of the kgd-net with tris-bischelating octahedral metal centers (MOF-888, CTH-7, CTH-10, Zn-MOF-888, CTH-11) we also in each layer see alternating clockwise propellers for the cpb ligand and anticlockwise for the likewise propeller-shaped metal complex (and vice versa). This is always matched by the opposite chirality in the next layer.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The theoretical part is a direct offspring of our structural analysis and related to our recent work on metal-oxalate topologies. 24 We were, among other things, intrigued by the absence in the literature of a 3D net combining hexagons and triangles, which led us to model building and the concept of foldable nets.…”

Section: Introductionmentioning

confidence: 99%

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Metal–Organic Frameworks with Hexakis(4-carboxyphenyl)benzene: Extensions to Reticular Chemistry and Introducing Foldable Nets

et al. 2020

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Nine metal–organic frameworks have been prepared with the hexagon-shaped linker 1,2,3,4,5,6-hexakis(4-carboxyphenyl)benzene (H6cpb) by solvothermal reactions in dimethylformamide (dmf) or dimethylacetamide (dmac) with acetic acid or formic acid as modulators: [Bi2(cpb)(acetato)2(dmf)2]·2dmf CTH-6 forms a rtl-net; 2(H2NMe2)[Cu2(cpb)] CTH-7 forms a kgd-net; [Fe4(cpb)(acetato)2(dmf)4] CTH-8 and [Co4(cpb)(acetato)2(dmf)4] CTH-9 are isostructural and form yav-nets; 2(HNEt3)[Fe2(cpb)] CTH-10 and the two polymorphs of 2(H2NMe2)[Zn2(cpb)]·1.5dmac, Zn-MOF-888 and CTH-11, show kgd-nets; [Cu2(cpb)(acetato)2(dmf)2]·2dmf, CTH-12, forms a mixed coordination and hydrogen-bonded sql-net; and 2(H2NMe2)[Zn2(cpb)] CTH-13, a similarly mixed yav-net. Surface area values (Brunauer–Emmett–Teller, BET) range from 34 m2 g–1 for CTH-12 to 303 m2 g–1 for CTH-9 for samples activated at 120 °C in dynamic vacuum. All compounds show normal (10-fold higher) molar CO2 versus N2 uptake at 298 K, except the 19-fold CO2 uptake for CTH-12 containing Cu(II) dinuclear paddle-wheels. We also show how perfect hexagons and triangles can combine to a new 3D topology laf, a model of which gave us the idea of foldable network topologies, as the laf-net can fold into a 2D form while retaining the local geometry around each vertex. Other foldable nets identified are cds, cds-a, ths, sqc163, clh, jem, and tfc covering the basic polygons and their combinations. The impact of this concept on “breathing” MOFs is discussed. I2 sorption, both from gas phase and from MeOH solution, into CTH-7 were studied by time of flight secondary ion mass spectrometry (ToF-SIMS) on dried crystals. I2 was shown to have penetrated the crystals, as layers were consecutively peeled off by the ion beam. We suggest ToF-SIMS to be a method for studying sorption depth profiles of MOFs.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Metal–Organic Frameworks with Hexakis(4-carboxyphenyl)benzene: Extensions to Reticular Chemistry and Introducing Foldable Nets

et al. 2020

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“…COD is characterized by a zeolitic structure exhibiting a true structural challenge. It is considered as one of the very few natural MOFs (Metal Organic Frameworks) (Huskic, 2016;Dazem et al, 2019) and its chemical formula is better represented by CaC2O4 . (2+x)H2O (x ≤ 0.5) (Petit et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

A novel multinuclear solid state NMR approach for the characterization of kidney stones

Leroy¹,

Bonhomme-Coury²,

Gervais³

et al. 2021

Preprint

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Abstract. The spectroscopic study of pathological calcifications (including kidney stones) is extremely rich and helps to improve the understanding of the physical and chemical processes associated with their formation. While FTIR imaging and optical/electron microscopies are routine techniques in hospitals, there has been a dearth of solid state NMR studies introduced into this area of medical research, probably due to the scarcity of this analytical technique in hospital facilities. This work introduces effective multinuclear and multi-dimensional solid state NMR methodologies to study the complex chemical and structural properties characterising kidney stone composition. As a basis for comparison three hydrates (n = 1, 2 and 3) of calcium oxalate are examined along with nine representative kidney stones. The multinuclear MAS NMR approach adopted investigates the 1H, 13C, 31P and 43Ca nuclei, with the 1H and 13C MAS NMR data able to be readily deconvoluted into the constituent elements associated with the different oxalates and organics present. For the first time, the full interpretation of highly resolved 1H NMR spectra is presented for the three hydrates, based on structure and local dynamics. The corresponding 31P MAS NMR data indicates the presence of low-level inorganic phosphate species, however the complexity of these data make the precise identification of the phases difficult to assign. This work provides physicians, urologists and nephrologists with additional avenues of spectroscopic investigation to interrogate this complex medical dilemma that requires real multi technique approaches to generate effective outcomes.

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“…and minerals [35,36]. Additionally, the use of this ligand in combination with Ln and An metals as a toolbox to obtain CPs dates back to the 1980s, where Kahwa et al [37] reported a family of isostructural 1D structures with the general formula K 3 [Ln(ox) 3 (OH 2 )]•2H 2 O, (Ln = Nd, Sm, Eu, Gd, Tb).…”

Section: Coordination Polymers Based On Oxalate Linkermentioning

confidence: 99%

Highlighting Recent Crystalline Engineering Aspects of Luminescent Coordination Polymers Based on F-Elements and Ditopic Aliphatic Ligands

2022

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Three principal factors may influence the final structure of coordination polymers (CPs): (i) the nature of the ligand, (ii) the type and coordination number of the metal center, and (iii) the reaction conditions. Further, flexible carboxylate aliphatic ligands have been widely employed as building blocks for designing and synthesizing CPs, resulting in a diverse array of materials with exciting architectures, porosities, dimensionalities, and topologies as well as an increasing number of properties and applications. These ligands show different structural features, such as torsion angles, carbon backbone number, and coordination modes, which affect the desired products and so enable the generation of polymorphs or crystalline phases. Additionally, due to their large coordination numbers, using 4f and 5f metals as coordination centers combined with aliphatic ligands increases the possibility of obtaining different crystal phases. Additionally, by varying the synthetic conditions, we may control the production of a specific solid phase by understanding the thermodynamic and kinetic factors that influence the self-assembly process. This revision highlights the relationship between the structural variety of CPs based on flexible carboxylate aliphatic ligands and f-elements (lanthanide and actinides) and their outstanding luminescent properties such as solid-state emissions, sensing, and photocatalysis. In this sense, we present a structural analysis of the CPs reported with the oxalate ligand, as the one rigid ligand of the family, and other flexible dicarboxylate linkers with –CH2– spacers. Additionally, the nature of the luminescence properties of the 4f or 5f-CPs is analyzed, and finally, we present a novel set of CPs using a glutarate-derived ligand and samarium, with the formula [2,2′-bipyH][Sm(HFG)2 (2,2′-bipy) (H2O)2]•(2,2′-bipy) (α-Sm) and [2,2′-bipyH][Sm(HFG)2 (2,2′-bipy) (H2O)2] (β-Sm).

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Natural and synthetic metal oxalates – a topology approach

Abstract: Network topology analysis is applied to a large number of mineral and synthetic oxalates, and is shown to be a superior method in describing and communicating the structure of these materials, including the first natural MOF weddellite.

Cited by 18 publications

References 35 publications

Metal–Organic Frameworks with Hexakis(4-carboxyphenyl)benzene: Extensions to Reticular Chemistry and Introducing Foldable Nets

Metal–Organic Frameworks with Hexakis(4-carboxyphenyl)benzene: Extensions to Reticular Chemistry and Introducing Foldable Nets

A novel multinuclear solid state NMR approach for the characterization of kidney stones

Highlighting Recent Crystalline Engineering Aspects of Luminescent Coordination Polymers Based on F-Elements and Ditopic Aliphatic Ligands

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