Thermal-, pressure- and light-induced spin-crossover behviour in the two-dimensional Hofman-like coordination polymer [Fe(3-Clpy)2Pd(CN)4]
The thermal spin-crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure-induced spincrossover behaviour at 298 K are discussed for the non-porous two-dimensional Hofmann-like coordination polymer [Fe(3-Clpy)(2)Pd(CN)(4)] (1). The title compound undergoes a two-step, cooperative thermal-induced SCO with critical temperatures T-c1(down arrow) = 159.6 K and T-c1(up arrow) = 164.5 K for the first step and T-c2(down arrow) = 141.4 K and T-c2(up arrow) = 148.4 K for the second step. Irradiation of the low-spin state with green light (514 nm) at 10 K induced the photoexcitation of around 60% of the iron(II) centres to the high-spin state (LIESST effect). The subseq…
The Effect of Pressure on the Cooperative Spin Transition in the 2D Coordination Polymer {Fe(phpy) 2 [Ni(CN) 4 ]}
The effect of pressure on the spin-transition properties of the 2D coordination polymer {Fe(phpy)2[Ni(CN)4]} is reported. The study has been carried out by means of variable-temperature (10–310 K) magnetic susceptibility measurements at applied pressures of 105 Pa to 1.0 GPa and spectroscopic studies in the visible region at room temperature (105 Pa–3.0 GPa). As the pressure is increased, the characteristic temperature of the spin transition is displaced to higher temperatures and the thermal hysteresis loop disappears. A cooperative first-order spin transition characterized by a piezo-hysteresis loop about 0.3 GPa wide was observed at 293 K.
Pressure Effect Studies on the Spin Transition of Microporous 3D Polymer [Fe(pz)Pt(CN)4]
Pressure effects on the spin transition of the three-dimensional (3D) porous coordination polymer {Fe(pz)[Pt(CN)4]} have been investigated in the interval 105 Pa–1.0 GPa through variable-temperature (10–320 K) magnetic susceptibility measurements and spectroscopic studies in the visible region at room temperature. These studies have disclosed a different behavior of the compound under pressure. In the magnetic experiments, a temperature independent paramagnetic behavior has been observed under 0.4 GPa. In contrast, at room temperature and at 0.8 GPa, a complete HS-to-LS transition has been evidenced. The differences in the magnetic behavior are strongly related with the porous structure of …
Synthesis and Characterisation of a New Series of Bistable Iron(II) Spin-Crossover 2D Metal-Organic Frameworks
Twelve coordination polymers with formula {Fe(3-Xpy)(2)[M(II)(CN)(4)]} (M(II): Ni, Pd, Pt; X: F, Cl, Br, I; py: pyridine) have been synthesised, and their crystal structures have been determined by single-crystal or powder X-ray analysis. All of the fluoro and iodo compounds, as well as the chloro derivative in which M(II) is Pt, crystallise in the monoclinic C2/m space group, whereas the rest of the chloro and all of the bromo derivatives crystallise in the orthorhombic Pnc2 space group. In all cases, the iron(II) atom resides in a pseudo-octahedral [FeN(6)] coordination core, with similar bond lengths and angles in the various derivatives. The major difference between the two kinds of str…
Electrical Voltage Control of the Pressure-Induced Spin Transition at Room Temperature in the Microporous 3D Polymer [Fe(pz)Pt(CN)4]
Fine control and direct monitoring of the spin crossover properties driven by pressure at room temperature are reported for the porous three-dimensional coordination polymer {Fe(pz)[Pt(CN)4]} by us...