Tuning the Structural and Magnetic Properties of Thermally Robust Coordination Polymers

Masciocchi, Norberto; Galli, Simona; Sironi, Angelo; Cariati, Elena; Galindo, Miguel A.; Barea, Elisa; Romero, M. Angustias; Salas, Juan M.; Navarro, Jorge A. R.; Santoyo‐González, Francisco

doi:10.1021/ic0602188

Cited by 33 publications

(27 citation statements)

References 49 publications

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“…[24] Finally, the [{M(5-X-2-pymo) 2 } n ] species (X = Cl, Br, I), which are isomorphous and of the diamondoid type, possess non-negligible, stabilising O···X interactions that have been used to interpret their whole structure and thermal stability. [13] Evidently, the same interactions cannot be at work in the case of the F-containing derivatives, which adopt the sodalitic or layered structures above described.…”

Section: à3mentioning

confidence: 98%

“…[13] Likewise, the high-temperature behaviour of the dc magnetic susceptibility for g-Co is typical of an antiferromagnetic material with a maximum at about 18 K and the c M T values showing a smooth decrease from 1.74 cm 3 mol À1 K at 250 K to 0.56 cm 3 mol À1 K at 18 K. Its susceptibility data have been fit to the Curie-Weiss equation, c M = C/A C H T U N G T R E N N U N G (TÀq), with C = 1.94(1) cm 3 K mol À1 and q = À32.4(4) K. For both compounds, the behaviour described is due to the antiferromagnetic coupling of the cobalt(II) centres transmitted through the N,N'-and N,O-F-pymo bridges. Alternatively, the magnetic behaviour of g-Co can be reasonably interpreted through Equation (1), which is adequate to describe the high-temperature dependence of c M T on a 2D Heisenberg quadratic network of spins.…”

Section: Gas Adsorption Propertiesmentioning

confidence: 99%

“…[10,11] In this context, we have recently prepared and characterised a number of zeolitic PCPs of [{MA C H T U N G T R E N N U N G (pymo) 2 } n ] formula, based on the deprotonated hydroxypyrimidine (Hpymo) ligands. Metal variation and ligand substitution have been explored as a way to tune the structural aspects and the functional properties of these materials, leading to the discovery of dense 2D and 3D [{MA C H T U N G T R E N N U N G (X-pymo) 2 } n ] polymeric species (M = Co, Zn; X-pymo = 5-X-pyrimidin-2-olate; X = NO 2 , [12] Cl, Br, I [13] ), or of porous materials, for example, the sodalitic [{CuA C H T U N G T R E N N U N G (H-pymo) 2 } n ] [14] and [{PdA C H T U N G T R E N N U N G (X-pymo) 2 } n ] (X= H, F) [15] materials, and the gismondine-like [{CuA C H T U N G T R E N N U N G (F-pymo) 2 } n ] [16] one. It is worth noting the solid-gas adsorptive properties of the last system, which gives rise to an unusual ordering of the stored gas molecules related to their ultramicroporous nature.…”

Section: Introductionmentioning

confidence: 99%

“…Lower thermal stabilities are observed for the halo or nitro substitution, with the I-pymo species showing decomposition temperatures below 673 K, which has been attributed to the intrinsic lability of the I-arene bond. [13] Crystal structures of the a-phases: The isomorphous a-Co and a-Zn compounds crystallise in the trigonal R3m space group. The asymmetric unit is composed of one metal centre, in a general position, one F-pymo ligand in a general position, two F-pymo ligands about a crystallographic mirror plane (b Wyckoff position)-giving a total of two ligands per asymmetric unit-and four water molecules, one in a general position and the other three about a crystallographic mirror plane-giving a total of two and a half water molecules per asymmetric unit.…”

mentioning

confidence: 99%

“…, [15] anhydrous [{CuA C H T U N G T R E N N U N G (Hpymo) 2 } n ] [14] ), trigonal (hydrated [{CuA C H T U N G T R E N N U N G (H-pymo) 2 } n ], [14] a-Co, a-Zn) and tetragonal ([{CoA C H T U N G T R E N N U N G (X-pymo) 2 } n ] and [{ZnA C H T U N G T R E N N U N G (Xpymo) 2 } n ] X= H, [20] Cl, Br, I; [13] [{CuA C H T U N G T R E N N U N G (F-pymo) 2 } n ] [16] ). In the following, to derive a comparative structural analysis involving the title compounds, we will focus the discussion on the cubic and trigonal materials.…”

mentioning

confidence: 99%

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Polymorphic Coordination Networks Responsive to CO₂, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Galli

Masciocchi

Tagliabue

et al. 2008

Chemistry A European J

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The novel porous [{M(F-pymo)(2)}(n)]2.5n H(2)O coordination networks (M=Co, Zn; F-pymo=5-fluoropyrimidin-2-olate), possessing sodalitic topology, have been synthesised and structurally characterised by means of powder diffraction methods. Thermodiffractometry demonstrated their plasticity: when heated up to 363 K, they reversibly transform into three-dimensional dehydrated [{M(F-pymo)(2)}(n)] species, with significantly different lattice parameters. Further heating induces irreversible polymorphic transformations into layered phases, in which the original MN(4) coordination sphere changes into an MN(3)O one. A mixed-metal phase, [{Co(x)Zn(1-x)(F-pymo)(2)}(n)]2.5n H(2)O, was also prepared, showing that zinc is preferentially inserted, when starting from a Co/Zn reagent ratio of 1:1. The solid-gas adsorption properties of the anhydrous 3D frameworks have been explored towards N(2), H(2) (77 K) and CH(4), CO(2) (273 K). These results show that these materials permit the diffusion of CO(2) molecules only. Remarkably, the CO(2) adsorption process for the [{Co(F-pymo)(2)}(n)] network proceeds in two steps: the first step takes place at low pressures (<600 kPa) and the second one above a threshold pressure of 600 kPa. By contrast, the [{Zn(F-pymo)(2)}(n)] network only permits CO(2) diffusion by applying pressures above 900 kPa. This type of behaviour is typical of porous networks with gated channels. The high CO(2) selectivity of these systems over the rest of the essayed probe gases is explained in terms of flexibility and polarity of the porous network. Finally, the magnetic studies on the Co(II) systems reveal that the as synthesised [{Co(F-pymo)(2)}(n)]2.5n H(2)O material behaves as an antiferromagnet with a T(N) of about 29 K. At variance, the [{Co(F-pymo)(2)}(n)] layered phase shows an unusually weak ferromagnetic ordering below 17 K, arising from a spin-canting phenomenon.

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Section: à3mentioning

confidence: 98%

Section: Gas Adsorption Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Polymorphic Coordination Networks Responsive to CO₂, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Galli

Masciocchi

Tagliabue

et al. 2008

Chemistry A European J

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Zeolitelike Metal–Organic Frameworks ( ZMOFs ): Design, Structure, and Properties

Alkordi¹,

Eddaoudi²

2012

Supramolecular Chemistry

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The quest for functional materials targeted at specific applications is ever increasing as societal needs and demands mount with advancing technology. One class of inorganic‐organic hybrid materials, metal‐organic materials (MOMs), has burgeoned in recent years due, in part, to effective design strategies (e.g., reticular chemistry) for their synthesis and their inherent (and readily interchangeable) hybrid, highly functional character. The molecular building block (MBB) approach introduces the ability to generate rigid and directional building blocks, mostly in situ , for the construction of MOMs having specific underlying networks and/or targeted functions/properties. Various MBBs can be targeted and utilized in the assembly of functional MOMs: (i) single‐metal‐ion‐based MBBs, which promote rational construction, by forcing rigidity and directionality through control of the metal coordination sphere and judicious selection of suitable heterofunctional (N‐, O‐coordination) organic ligands, of porous MOMs with extralarge cavities, including zeolitelike metal‐organic frameworks (ZMOFs); (ii) multinuclear metal‐cluster‐based MBBs, where, for example, simple metal‐carboxylate clusters possess multiple metal‐oxygen coordination bonds that result in the generation of rigid nodes with fixed geometry that, when combined with organic ligands of specific geometry, lead to the construction of desired MOMs; and (iii) supermolecular building blocks (SBBs), which involve enhanced built‐in directional and structural information (e.g., high degree of symmetry and connectivity) compared to simple MBBs and allow the construction of high‐connectivity nets (e.g., rht‐MOFs). The MBB approach and associated strategies, as well as physical properties of some corresponding MOMs, are presented.

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Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

Espallargas

2010

Ideas in Chemistry and Molecular Sciences

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The ultimate goal of a solid-state chemist is the rational design and synthesis of crystalline materials with the presence of specific and tunable chemical or physical properties, the so-called ''smart materials.'' Porosity, magnetism, chirality, conductivity, superconductivity, spin-transition, optical, and photophysical properties can be exploited for a wide variety of applications including gas storage, separations, electronic, catalysis, nonlinear optics, or drug delivery, and are therefore the objectives of intense research activity. The occurrence of these properties in crystalline materials 1) results from the combination of two aspects: (i) the molecular units (building blocks) that compose the crystal and (ii) the arrangement of these building blocks in the crystal. Controlling the former is relatively simple, and essentially it is only limited to the imagination and creativity of the researcher, since molecular chemistry has, over about two centuries, developed a wide range of very powerful procedures for creating even more sophisticated molecules from atoms linked by covalent bonds. On the contrary, organizing the molecules, or building blocks, in a predetermined manner is difficult to accomplish given that the structure of crystalline solids results from a delicate balance between all the intermolecular interactions present in the crystal, maximizing the attractive ones and minimizing the repulsive ones while, although not always, adopting the densest packing [1]. When a single strong interaction dominates in the system other weak intermolecular interactions normally play a secondary role in the crystal packing, providing support to the stronger interactions. In this situation, control over the molecular packing can successfully be achieved [2], although the presence of numerous weak interactions can in some cases overwhelm much stronger interactions as a result of their abundance [3]. Further difficulties can be encountered if the building blocks are 1) It should of course be acknowledged that crystalline products might not always represent the most desirable form of a material with respect to a given application.

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Tuning the Structural and Magnetic Properties of Thermally Robust Coordination Polymers

Cited by 33 publications

References 49 publications

Polymorphic Coordination Networks Responsive to CO₂, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Polymorphic Coordination Networks Responsive to CO₂, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Zeolitelike Metal–Organic Frameworks ( ZMOFs ): Design, Structure, and Properties

Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

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Tuning the Structural and Magnetic Properties of Thermally Robust Coordination Polymers

Cited by 33 publications

References 49 publications

Polymorphic Coordination Networks Responsive to CO2, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Polymorphic Coordination Networks Responsive to CO2, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Zeolitelike Metal–Organic Frameworks ( ZMOFs ): Design, Structure, and Properties

Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

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Product

Resources

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Polymorphic Coordination Networks Responsive to CO₂, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Polymorphic Coordination Networks Responsive to CO₂, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates