Unraveling the Guest-Induced Switchability in the Metal-Organic Framework DUT-13(Zn)

A guest-induced flexibility in the framework DUT-13 was investigated in situ to analyze the breathing mechanism upon physisorption of nitrogen (77 K) and n-butane (273 K). The crystal structure of cp phase, solved from PXRD data using the computation-assisted semiempirical approach, shows two times smaller pore volume, compared to the op phase, which is consistent with the corresponding isotherms. The contraction mechanism is mainly based on the conformational isomerism of the benztb4- linker, which transforms from a staggered conformation in op phase to a more eclipsed in cp phase, leading to the contraction of the larger pore. A nearly complete op → cp → op transition was observed in the case of n-butane adsorption at 273 K, while in case of weakly interacting nitrogen molecules a portion of the sample remains in the op phase in the entire pressure range. Apparently, in case of DUT-13 the contraction is crystallite size-dependent, similarly as in a number of other switchable MOFs, which should be investigated more in detail in the future. Methane adsorption at varying temperatures showed a wide hysteresis at the temperatures between 111 K and 140 K. The hysteresis width decreases until it disappears completely at 170 K leading to a reversible isotherm, typical for rigid frameworks. The fact that breathing is observed in a broader temperature range in comparison to DUT‑49 demonstrates that thermodynamics and kinetics favour the DUT-13 contraction. Linker and hinges in DUT-13 are not stiff enough to support the metastable states required for NGA.

Unraveling the Guest-Induced Switchability in the Metal-Organic Framework DUT-13(Zn)

A guest-induced flexibility in the framework DUT-13 was investigated in situ to analyze the breathing mechanism upon physisorption of nitrogen (77 K) and n-butane (273 K). The crystal structure of cp phase, solved from PXRD data using the computation-assisted semiempirical approach, shows two times smaller pore volume, compared to the op phase, which is consistent with the corresponding isotherms. The contraction mechanism is mainly based on the conformational isomerism of the benztb4- linker, which transforms from a staggered conformation in op phase to a more eclipsed in cp phase, leading to the contraction of the larger pore. A nearly complete op → cp → op transition was observed in the case of n-butane adsorption at 273 K, while in case of weakly interacting nitrogen molecules a portion of the sample remains in the op phase in the entire pressure range. Apparently, in case of DUT-13 the contraction is crystallite size-dependent, similarly as in a number of other switchable MOFs, which should be investigated more in detail in the future. Methane adsorption at varying temperatures showed a wide hysteresis at the temperatures between 111 K and 140 K. The hysteresis width decreases until it disappears completely at 170 K leading to a reversible isotherm, typical for rigid frameworks. The fact that breathing is observed in a broader temperature range in comparison to DUT‑49 demonstrates that thermodynamics and kinetics favour the DUT-13 contraction. Linker and hinges in DUT-13 are not stiff enough to support the metastable states required for NGA.

Shape Memory Effect of Polycrystalline Ni54Mn25Ga17.5Ta0.5 High Temperature Shape Memory Alloy with Wide Hysteresis Loop

Effect of Ta-alloying on microstructure, martensitic transformation, mechanical property and shape memory effect of Ni54Mn25Ga17.5Ta0.5 alloy has been systematically investigated. The results show that the substructure of Ni-Mn-Ga alloy significantly changed, which was converted from the plate martensite to the lath martensite. Compression tests show that a compressive strength of 1380 MPa with a fracture strain up to 21.92% can be achieved in the Ni54Mn25Ga17.5Ta0.5 alloy at room temperature. This is no changed martensite structure with non-modulated T martensite. In addition, the martensitic transition temperature obviously decreases from 350 °C to 208 °Cand hysteresis loop increases about 20 °Cwhen Ta substituted of Ni. The shape memory effect increased with the increase of pre-deformation, nevertheless, the shape recovery ratio appeared firstly increases and then decreases. When the pre-deformation is 10%, 15%, 20%, the shape memory effect of the alloy is 5.1%, 6.8% and 10%, respectively.

Iron(II) Spin Crossover Complexes with 4,4′-Dipyridylethyne—Crystal Structures and Spin Crossover with Hysteresis

Three new iron(II) 1D coordination polymers with cooperative spin crossover behavior showing thermal hysteresis loops were synthesized using N2O2 Schiff base-like equatorial ligands and 4,4′-dipyridylethyne as a bridging, rigid axial linker. One of those iron(II) 1D coordination polymers showed a 73 K wide hysteresis below room temperature, which, upon solvent loss, decreased to a still remarkable 30 K wide hysteresis. Single crystal X-ray structures of two iron(II) coordination polymers and T-dependent powder XRD patterns are discussed to obtain insight into the structure property relationship of those materials.

Increasing spin crossover cooperativity in 2D Hofmann-type materials with guest molecule removal

Ambient temperature spin crossover with wide hysteresis has been achieved in 2D Hofmann-type materials, where removal of guest molecules optimises ligand–ligand interactions, resulting in increased cooperativity.

Tuning the spin crossover behavior of the polyanion [(H2O)6Fe3(μ-L)6]6–: the case of the cesium salt

Cation exchange transforms the gradual spin transition of the trimer [(H2O)6Fe3(μ-L)6]6– into an abrupt transition with a wide hysteresis above room temperature.

Hysteretic spin crossover driven by anion conformational change

An air stable FeIII complex showing a wide hysteresis near room temperature is described. The origin of the cooperativity is an unprecedented anion conformational change.

Solvent modified spin crossover in an iron(iii) complex: phase changes and an exceptionally wide hysteresis

The impact of solvent on spin crossover is explored with T1/2 varying by 200 K and hysteresis up to 80 K.

Iron(ii) spin crossover complexes with diaminonaphthalene-based Schiff base-like ligands: 1D coordination polymers

Iron(ii) spin crossover coordination polymers with diaminonaphthalene derived Schiff base-like ligands were synthesised, and their magnetic and structural properties were analysed. Rigid bridging ligands having up to 40 K wide hysteresis loops were observed.