Four-step iron(ii) spin state cascade driven by antagonistic solid state interactions.

A four-stepped cascade of Fe(ii) high spin (HS) to low spin (LS) states is demonstrated in a family of 2-D Hofmann materials, [Fe(saltrz)(M(CN))]·8(HO) (M = Pd ( ), Pt ( ); saltrz = ()-2-(((4-1,2,4-triazol-4-yl)imino)methyl)phenol). Alongside the fully HS and LS Fe(ii) states, fractional spin state stabilization occurs at HS/LS values of 5/6, 2/3, and 1/6. This unconventional spin state periodicity is driven by the presence of multiple spin crossover (SCO) active Fe(ii) sites which are in subtly distinct environments driven by a network of antagonistic host-host and host-guest interactions.

Exploiting Pressure To Induce a "Guest-Blocked" Spin Transition in a Framework Material.

A new functionalized 1,2,4-triazole ligand, 4-[(E)-2-(5-methyl-2-thienyl)vinyl]-1,2,4-triazole (thiome), was prepared to assess the broad applicability of strategically producing multistep spin transitions in two-dimensional Hofmann-type materials of the type [FePd(CN)(R-1,2,4-trz)]·nHO (R-1,2,4-trz = a 4-functionalized 1,2,4-triazole ligand). A variety of structural and magnetic investigations on the resultant framework material [FePd(CN)(thiome)]·2HO (A·2HO) reveal that a high-spin (HS) to low-spin (LS) transition is inhibited in A·2HO due to a combination of guest and ligand steric bulk effects. The water molecules can be reversibly removed with retention of the porous host framework and result in the emergence of an abrupt and hysteretic one-step spin transition due to the removal of guest internal pressure.

Correction: Hydrophobic pillared square grids for selective removal of CO2 from simulated flue gas.

Correction for 'Hydrophobic pillared square grids for selective removal of CO2 from simulated flue gas' by Sameh K. Elsaidi et al., Chem.

Hydrophobic pillared square grids for selective removal of CO2 from simulated flue gas.

Capture of CO2 from flue gas is considered to be a feasible approach to mitigate the effects of anthropogenic emission of CO2. Herein we report that an isostructural family of metal organic materials (MOMs) of general formula [M(linker)2(pillar)], linker = pyrazine, pillar = hexaflourosilicate and M = Zn, Cu, Ni and Co exhibits highly selective removal of CO2 from dry and wet simulated flue gas. Two members of the family, M = Ni and Co, SIFSIX-3-Ni and SIFSIX-3-Co, respectively, are reported for the first time and compared with the previously reported Zn and Cu analogs.

Understanding the Adsorption Mechanism of Xe and Kr in a Metal-Organic Framework from X-ray Structural Analysis and First-Principles Calculations.

Enhancement of adsorption capacity and separation of radioactive Xe/Kr at room temperature and above is a challenging problem. Here, we report a detailed structural refinement and analysis of the synchrotron X-ray powder diffraction data of Ni-DODBC metal organic framework with in situ Xe and Kr adsorption at room temperature and above. Our results reveal that Xe and Kr adsorb at the open metal sites, with adsorption geometries well reproduced by DFT calculations.

Pressure-induced structural phase transformation in cobalt(II) dicyanamide.

In situ synchrotron powder diffraction has been used to probe the pressure-dependent structural properties of the magnetic molecular framework material Co(dca)2 [dca = dicyanamide or N(CN)2(-)]. An orthorhombic (Pmnn) to monoclinic (P2₁/n) transformation to a high-pressure phase, namely γ-Co(dca)2, occurs at 1.1 GPa.

In situ studies of a platform for metastable inorganic crystal growth and materials discovery.

Rapid shifts in the energy, technological, and environmental demands of materials science call for focused and efficient expansion of the library of functional inorganic compounds. To achieve the requisite efficiency, we need a materials discovery and optimization paradigm that can rapidly reveal all possible compounds for a given reaction and composition space. Here we provide such a paradigm via in situ X-ray diffraction measurements spanning solid, liquid flux, and recrystallization processes.

Exploiting high pressures to generate porosity, polymorphism, and lattice expansion in the nonporous molecular framework Zn(CN)2.

Systematic exploration of the molecular framework material Zn(CN)2 at high pressure has revealed several distinct series of transitions leading to five new phases: four crystalline and one amorphous. The structures of the new crystalline phases have been resolved through ab initio structural determination, combining charge flipping and direct space methods, based on synchrotron powder diffraction data. The specific transition activated under pressure depends principally on the pressure-transmitting fluid used.

Reversible switching from antiferro- to ferromagnetic behavior by solvent-mediated, thermally-induced phase transitions in a trimorphic MOF-based magnetic sponge system.

Hydrothermal reactions of copper(II) acetate, tetrazolate-5-carboxylate (tzc), and the neutral N-donor spacer ligand 1,3-di(4-pyridyl)propane (dpp) lead in a single reaction vial to the simultaneous formation of three different single-crystalline solvates [Cu(tzc)(dpp)]n·0.5C6H14·0.5H2O (1), [Cu(tzc)(dpp)]n·4.

Chemical bonding and magnetic exchange in two-dimensional [M(TCNE)(NCMe)2]X (M = Fe, Mn; X = FeCl4, SbF6) magnets: a pressure study.

Pressure-dependent X-ray diffraction studies reveal the bulk modulus and compression anisotropy of the 2D magnet [Mn(TCNE)(NCMe)(2)]SbF(6). The Raman response of this and the similar [Fe(TCNE)(NCMe)(2)]FeCl(4) layered magnet, shows that the evolution of the a(g) ν(C=C) frequency correlates well with the magnetic exchange and T(c) variations of these materials under pressure. There is a significantly more complex correlation between the a(g) ν(C≡N) frequency and T(c) despite the fact that some unpaired π* electron density (~0.

Low-energy selective capture of carbon dioxide by a pre-designed elastic single-molecule trap.

Single-molecule trap: Easy activation of the water-stable metal-organic framework PCN-200 provides a new route to low-energy selective CO(2) capture through stimuli-responsive adsorption behavior. This elastic CO(2) trapping effect was confirmed by single-component and binary gas-adsorption isotherms and crystallographic determination.

Importance of halogen···halogen contacts for the structural and magnetic properties of CuX2(pyrazine-N,N′-dioxide)(H2O)2 (X = Cl and Br).

The structural and magnetic properties of the newly crystallized CuX(2)(pyzO)(H(2)O)(2) (X = Cl, Br; pyzO = pyrazine-N,N'-dioxide) coordination polymers are reported. These isostructural compounds crystallize in the monoclinic space group C2/c with, at 150 K, a = 17.0515(7) Å, b = 5.

Trapping guests within a nanoporous metal-organic framework through pressure-induced amorphization.

The release of guest species from within a nanoporous metal-organic framework (MOF) has been inhibited by amorphization of the guest-loaded framework structure under applied pressure. Thermogravimetric analyses have shown that by amorphizing ZIF-8 following sorption of molecular I(2), a hazardous radiological byproduct of nuclear energy production, the pore apertures in the framework are sufficiently distorted to kinetically trap I(2) and improve I(2) retention. Pair distribution function (PDF) analysis indicates that the local structure of the captive I(2) remains essentially unchanged upon amorphization of the framework, with the amorphization occurring under the same conditions for the vacant and guest-loaded framework.

Spectroscopic study of (two-dimensional) molecule-based magnets: [M(II)(TCNE)(NCMe)2][SbF6] (M = Fe, Mn, Ni).

The M-[TCNE] (M = 3d metal; TCNE = tetracyanoethylene) system is one of the most interesting classes of molecule-based magnets, exhibiting a plethora of compositions and structures (inorganic polymer chains, 2D layers, 3D networks, and amorphous solids) with a wide range of magnetic ordering temperatures (up to 400 K). A systematic study of vibrational (both infrared and, for the first time, Raman) properties of the family of new TCNE-based magnets of M(II)(TCNE) (NCMe)(2)[SbF(6)] [M = Mn, Fe, Ni] composition is discussed in conjunction with their magnetic behavior and newly reso-lved crystal structures. The vibrational properties of the isolated TCNE(●-) anion in the paramagnetic Bu(4)N [TCNE(●-)] salt and recently characterized 2D layered magnet Fe(II)(TCNE)(NCMe)(2)[FeCl(4)] are also reported for comparison.

Elucidating the structure of surface acid sites on γ-Al2O3.

Differential pair distribution function analysis was applied to resolve, with crystallographic detail, the structure of catalytic sites on the surface of nanoscale γ-Al(2)O(3). The structure was determined for a basic probe molecule, monomethylamine (MMA), bound at the minority Lewis acid sites. These active sites were found to be five-coordinate, forming distorted octahedra upon MMA binding.

Zero thermal expansion in a flexible, stable framework: tetramethylammonium copper(I) zinc(II) cyanide.

Tetramethylammonium copper(I) zinc(II) cyanide, which consists of N(CH(3))(4)(+) ions trapped within a cristobalite-like metal cyanide framework, has been studied by variable-temperature powder and single-crystal X-ray diffraction. Its coefficient of thermal expansion is approximately zero over the temperature range 200-400 K and comparable with the best commercial zero thermal expansion materials. The atomic displacement parameters, apparent bond lengths, and structure of a low-temperature, low-symmetry phase reveal that the low-energy vibrational modes responsible for this behavior maintain approximately rigid Zn coordination tetrahedra but involve significant distortion of their Cu counterparts.

Pressure-induced amorphization and porosity modification in a metal-organic framework.

The impact of modest, industrially accessible pressures (0-1.2 GPa) on the structure and porosity of the zeolitic imidazolate framework Zn(2-methylimidazole)(2), ZIF-8, was investigated using in situ powder X-ray diffraction in combination with sorption measurements for pressure-treated samples. The framework is highly compressible, with a bulk modulus (K = -V partial differential P/partial differential V) of 6.

Guest tunable structure and spin crossover properties in a nanoporous coordination framework material.

The electronic switching properties of the nanoporous spin crossover framework [Fe(NCS)(2)(bpbd)(2)] x x(guest), SCOF-2, can be rationally manipulated via sorption of a range of molecular guests (acetone, ethanol, methanol, propanol, 1-acetonitrile) into the 1-D channels of this material. Pronounced changes to the spin crossover properties are related directly to the steric and electronic influence of the individual guests: the degree of lattice cooperativity, as reflected in the abruptness of the transition and presence of hysteresis, is strongly influenced by the presence of cooperative host-guest interactions, and the temperature of the transition varies with guest polarity through a proposed electrostatic interaction.

Dynamic interplay between spin-crossover and host-guest function in a nanoporous metal-organic framework material.

The nanoporous metal-organic framework [Fe(pz)Ni(CN)(4)], 1 (where pz is pyrazine), exhibits hysteretic spin-crossover at ambient conditions and is robust to the adsorption and desorption of a wide range of small molecular guests, both gases (N(2), O(2), CO(2)) and vapors (methanol, ethanol, acetone, acetonitrile, and toluene). Through the comprehensive analysis of structure, host-guest properties, and spin-crossover behaviors, it is found that this pillared Hofmann system uniquely displays both guest-exchange-induced changes to spin-crossover and spin-crossover-induced changes to host-guest properties, with direct dynamic interplay between these two phenomena. Guest desorption and adsorption cause pronounced changes to the spin-crossover behavior according to a systematic trend in which larger guests stabilize the high-spin state and therefore depress the spin-crossover temperature of the host lattice.

A nanoscale molecular switch triggered by thermal, light, and guest perturbation.

Bottoms up! A discrete metallo-supramolecular nanoball (see picture), synthesized by using "bottom-up" methodologies, uniquely undergoes a solvent-sensitive, physically addressable electronic spin switching. The switching occurs by thermal, light, or solvent perturbation, where importantly it can be switched "on" or "off" by green or red laser irradiation, respectively.

Elucidating the mechanism of a two-step spin transition in a nanoporous metal-organic framework.

The nanoporous metal-organic framework, Fe(bpe)2(NCS)2 x 3(acetone), SCOF-4(Ac) (where bpe is 1,2-bis(4'-pyridyl)ethane), displays a two-step spin crossover (SCO) transition (65-155 K) that is sensitive to the presence of acetone guest molecules. Structural analyses have revealed a structural phase transition, from tetragonal (P42(1)c) to orthorhombic (P2(1)2(1)2), associated with the spin transition that defines a checkerboard-like ordering of spin sites at the high-spin:low-spin plateau. The reversible desorption of the acetone guest species is accompanied by a complex series of structural phase transitions that describe a dramatic flexing of the structure.

Poly[mu4-sulfido-tris(thiocyanato-kappaN)tris(mu3-1,2,4-triazolato-kappa(3)N(1):N(2):N(4))tetrazinc(II)]: a three-dimensional zinc sulfide coordination polymer.

The title compound, [Zn(4)(C(2)H(2)N(3))(3)(NCS)(3)S](n), is a three-dimensional coordination polymer consisting of tetrahedral SZn(4) clusters bridged by triazole ligands. In the tetrahedral unit, three Zn atoms are connected to six bridging triazolate ligands, whereas the fourth Zn atom (site symmetry 3m) is bonded to three terminal thiocyanate anions that protrude into the void space created by the Zn-triazolate network. The network prototype is simple cubic, but a strong distortion along a body diagonal and the imposition of a polar direction by the arrangement of the molecular constituents lead to the trigonal space group R3m.