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…

Pressure and Thermally Induced Spin Crossover in a 2D Iron(II) Coordination Polymer {Fe[bipy(ttr)2]}n

Using magnetic measurements and UV -visible spectroscopy we have studied the pressure influence on the spin crossover (SCO) properties of the 2D Fe (II) coordination polymer formulated {Fe[bipy(ttr) 2 ]} n . At variable temperature and fixed pressure, we have measured the magnetic property of this compound. Under different pressures and at room temperature, the visible spectroscopy has been observed. The magnetic experiment displays a two-step spin crossover behavior under pressure. The visible spectroscopic measurements at room temperature show a spin crossover with an asymmetric hysteresis at 0.4GPa.

Pressure Tunable Electronic Bistability in Fe(II) Hofmann-like Two-Dimensional Coordination Polymer [Fe(Fpz)2Pt(CN)4]: A Comprehensive Experimental and Theoretical Study

A comprehensive experimental and theoretical study of both thermal-induced spin transition (TIST) as a function of pressure and pressure-induced spin transition (PIST) at room temperature for the two-dimensional Hofmann-like SCO polymer [Fe(Fpz)2Pt(CN)4] is reported. The TIST studies at different fixed pressures have been carried out by magnetic susceptibility measurements, while PIST studies have been performed by means of powder X-ray diffraction, Raman, and visible spectroscopies. A combination of the theory of elastic interactions and numerical Monte Carlo simulations has been used for the analysis of the cooperative interactions in TIST and PIST studies. A complete (T, P) phase diagram…

Pressure- and temperature-induced valence tautomeric interconversion in a o-dioxolene adduct of a cobalt-tetraazamacrocycle complex

An electronic switch at the molecular level has been realized by using a class of ionic compounds of the formula [Co(L)(diox)]Y (L = tetraazamacrocyclic ligand, Y = mononegative anion). Such compounds undergo temperature- and pressure-induced intramolecular one-electron transfer equilibria. The transition temperature of interconversion varies with the nature of the counterions Y (Y = PF6, BPh4, I). Surprisingly the effect of the anion on the transition temperature is not only governed by its volume but also by its coulombic interaction.

Tunable Bistability in a Three-Dimensional Spin-Crossover Sensory- and Memory-Functional Material

Pressure effect on a novel spin transition polymeric chain compound

[Fe(hyptrz)3]A2·H2O (hyptrz = 4-(3′-hydroxypropyl)-1,2,4-triazole and A = 4-chlorobenzenesulfonate) represents a novel iron(II) polymeric chain compound. A discontinuous spin transition has been observed by temperature dependent magnetic susceptibility measurements. The spin transition curves are shifted from 181 K to 324 K as the pressure varies from 1 bar to 5.9 kbar. The shapes of these curves are not strongly modified, and this is interpreted as being due to effective cooperative interactions along the chain. This behaviour under pressure can be extended to the family of iron(II)-1,2,4-triazole polymeric chain spin crossover materials.

Pressure Effect Investigations on the Spin Crossover Systems{Fe[H 2 B(pz) 2 ] 2 (bipy)} and {Fe[H 2 B(pz) 2 ] 2 (phen)}

Pressure effect studies on the spin crossover behaviour of the mononuclear compounds {Fe[H2B(pz)2]2(bipy)}(1) and {Fe[H2B(pz)2]2(phen)}(2) have been performed in the range of 105 Pa–1.02 GPa at variable temperatures (100–310 K). Continuous spin transitions and displacement of its characteristic temperature has been observed for 1 with increasing pressure. Meanwhile the response of 2 under applied pressures is quite unexpected, and can only be understood in terms of a crystallographic phase transition or change in the bulk modulus of the compound. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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.

Synthesis, crystal structure and magnetic properties of bis[μ-bis(3-(pyridin-2-yl)-1,2,4-triazole-N′,N1,N2)] bis[triaqua nickel(II)] tetranitrate

Abstract A new dinuclear nickel(II) coordination compound of formula Ni2(Hpt)2(H2O)6(NO3)4 (Hpt=3-(pyridin-2-yl)-1,2,4-triazole) was synthesized. The structure was solved at 298 K by single-crystal X-ray analysis. Bisμ-bis(3-(pyridin-2-yl)-1,2,4-triazole-N′,N1,N2) bistriaqua nickel(II) tetranitrate (C14H24N12O18Ni2) crystallizes in the triclinic space group P-1, a=7.2266(1), b=9.9144(1), c=11.2647(1) A, α=66.854(1)°, β=74.000(1)°, γ=86.400(2)°, V=712.42(1) A3, Z=1 (dinuclear units), 2823 reflections (1 > 2σ(I)), R1=0.0442, wR2=0.1197. The Ni(II) ions are bridged by two neutral Hpt ligands coordinating via N1 and N2 in the equatorial plane, Ni(1)-Ni(1)′=4.098(1) A. The Hpt bridging mode is a…

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 …

A spin transition molecular material with a wide bistability domain.

International audience; [Fe(hyptrz)3](4-chloro-3-nitrophenylsulfonate)22 H2O (1; hyptrz=4-(3-hydroxypropyl)-1,2,4-triazole) has been synthesized and its physical properties have been investigated by several physical techniques including magnetic susceptibility measurements, calorimetry, and Mössbauer, optical, and EXAFS spectroscopy. Compound 1 exhibits a spin transition below room temperature, together with a very wide thermal hysteresis of about 50 K. This represents the widest hysteresis loop ever observed for an FeII-1,2,4-triazole spin transition material. The cooperativity is discussed on the basis of temperature-dependent EXAFS studies and of the structural features of a CuII analogu…

Pressure-induced electron transfer in ferrimagnetic Prussian blue analogs

M\"ossbauer and magnetic susceptibility measurements were performed under pressure on three Prussian blue analogs, ${\mathrm{K}}_{0.1}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.7}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ ${\mathrm{K}}_{0.28}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.76}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ and ${\mathrm{Cs}}_{0.7}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.9}\ensuremath{\cdot}16{\mathrm{H}}_{2}\mathrm{O}.$ A pressure-induced electron transfer ${\mathrm{Co}}^{2+}(S=\frac{3}{2})\ensuremath{-}{\mathrm{Fe}}^{3+}(S=\frac{1}{2})\ensuremath{\rightarrow}{\mathrm{Co}}^{3+}(S=0)\ensuremath{-}{\mathrm{Fe}}^{2+}(S=0)…

Pressure-Induced High Spin State in [Fe(btr)2(NCS)2]·H2O (btr = 4,4′-bis-1,2,4-triazole)

Application of hydrostatic pressure (≤ 10.5 kbar) on the two-dimensional spin transition compound [Fe(btr)2(NCS)2]·H2O (btr = 4,4‘-bis-1,2,4-triazole) results in an unexpected stabilization of the HS state. On release of the pressure, the HS state is found to be partially trapped. After thermal relaxation of the metastable HS state obtained by the LIESST effect (light-induced excited spin state trapping), a pure LS state is obtained in contrast to the pressure experiments. This different behavior supports a structural phase transition as the likely basis of the pressure-induced HS state.

Thermal-,Pressure-, and Light-Induced Spin Transition in Novel Cyanide-Bridged FeII-AgI Bimetallic Compounds with Three-Dimensional Interpenetrating Double Structures {FeIILx[Ag(CN)2]2}·G

[EN] Low-spin, high-spin and spin-transition behaviours have been observed for the doubly interpenetrating three-dimensional bimetallic compounds {Fe-II(pz)[Ag(CN)(2)](2)}.pz (pz= pyrazine), {Fe-II(4,4'-bipy)(2)[Ag(CN)(2)](2)} (4,4'-bipy-4,4'-bipyridine), and {Fe-II-(bpe)(2)[Ag(CN)(2)](2)} (bpe = bispyridylethylene), respectively. The single crystals of the bpe derivative undergo a spin transition with a large hysteresis loop at about 95 K. After several warming and cooling cycles, the single crystals become a microcrystalline powder with 50% spin transition. Influence of pressure- as well as light-induced excited spin-state trapping (LIESST) on the thermal 50% spin transition of the microc…

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…

Variable Cooperative Interactions in the Pressure and Thermally Induced Multistep Spin Transition in a Two-Dimensional Iron(II) Coordination Polymer

Two types of experiments conducted to investigate the effect of pressure on the spin crossover (SCO) properties of the 2D Fe(II) coordination polymer formulated {Fe[bipy(ttr)2]}n are reported, namely, (1) magnetic measurements performed at variable temperature and at fixed pressure and (2) visible spectroscopy at variable pressure and fixed temperature. The magnetic experiments carried out under a hydrostatic pressure constraint of 0.04, 0.08, and 0.8 GPa reveal a two-step spin transition behavior. The characteristic critical temperatures of the spin transition are shifted upward in temperature as pressure increases. The slope of the straight-line of the Tc vs P plot, dTc/dP, is 775 K/GPa a…

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...

Pressure-induced cooperative spin transition in ironII 2D coordination polymers: room-temperature visible spectroscopic study.

For the 2D coordination polymers [Fe(3-Fpy)(2)M(II)(CN)(4)] (M(II) = Ni, Pd, Pt), the pressure-induced spin crossover behavior has been investigated at 298 K by monitoring the distinct optical properties associated with each spin state. Cooperative first-order spin transition characterized by a piezohysteresis loop ca. 0.1 GPa wide was observed for the three derivatives. Application of the mean field regular solution theory has enabled estimation of the cooperative parameter, Γ(p), and the enthalpy, ΔH(HL)(p), associated with the spin transition for each derivative. These values, found in the intervals 6.8-7.9 and 18.6-20.8 kJ mol(-1), respectively, are consistent with those previously repo…

Pressure-tuning of magnetism and linkage isomerism in iron(II) hexacyanochromate.

A pressure-induced linkage isomerization of the cyanide anion has been observed in single crystals of a chromium(III)-iron(II) Prussian blue analogue of formula K0.4Fe4[Cr(CN)6]2.8 square1.2.16H2O (1). Upon application of pressure in the 0-1200 MPa range, the cyanide ligand rotates and becomes C-bonded to the iron(II) cations, leading to a stabilization of their diamagnetic low-spin states. The result is a decrease of magnetization and magnetic ordering temperatures from TC = 19 K at ambient pressure to 13 K at 1200 MPa. The initial magnetic properties can be restored on pressure release. The reversible movement of cyanide in the solid state can be exploited as a switch of the magnetic inte…

Spin crossover behaviour in the iron(II)-2,2-dipyridilamine system: Synthesis, X-ray structure and magnetic studies

Abstract The monomeric compounds [Fe(dpa)2(X)2] · solv [X = NCS−(solv = 0.5H2O) (1), N ( CN ) 2 - (2) and dpa = 2,2-dipyridilamine] have been synthesised and characterised. They crystallise in the P21/n and in the Cc monoclinic systems, respectively. Four of six nitrogen atoms coordinated to the Fe(II) ions belong to two dpa ligands which lie in cis conformation. The remaining positions are occupied by two nitrogen atoms of the pseudo-halide ligands. The magnetic susceptibility measurements at ambient pressure have revealed that compound 1 exhibits an incomplete spin crossover behaviour (T1/2 ≈ 88 K), whereas compound 2 remains in the high-spin configuration. Pressure studies performed on c…

CCDC 1427507: Experimental Crystal Structure Determination

Related Article: Eugenio Coronado, M. Carmen Giménez-López, Tomasz Korzeniak, Georgiy Levchenko, Francisco M. Romero, Alfredo Segura, Valentín García-Baonza, Julio C. Cezar, Frank M. F. de Groot, Alla Milner, Moshe Paz-Pasternak|2008|J.Am.Chem.Soc.|130|15519|doi:10.1021/ja8047046

CCDC 1427488: Experimental Crystal Structure Determination

Related Article: Eugenio Coronado, M. Carmen Giménez-López, Tomasz Korzeniak, Georgiy Levchenko, Francisco M. Romero, Alfredo Segura, Valentín García-Baonza, Julio C. Cezar, Frank M. F. de Groot, Alla Milner, Moshe Paz-Pasternak|2008|J.Am.Chem.Soc.|130|15519|doi:10.1021/ja8047046