Synthesis, Crystal Structure and Magnetic Properties of [Fe(bpe)4(H2O)2](TCNQ)2 (bpe = trans-1,2-bis(4-pyridyl)ethane and TCNQ = tetracyanoquinodimethane)

The synthesis, structure and magnetic properties of [Fe(bpe)4(H2O)2](TCNQ)2 (1) are reported. 1 crystallizes in the triclinic P space group, a = 13.481(5), b = 14.887(3), c = 16.663(4) A, α = 101.048(18), β = 112.84(2), γ = 90.92(2)°, V = 3009.6(14) A3, Z = 2. The iron atom defines a compressed octahedron with the equatorial positions occupied by the bpe molecules which act as monodentate ligands and the two axial positions occupied by water molecules. The TCNQ− radical counterions are uncoordinated and interact by pairs defining (TCNQ)22− units strongly coupled antiferromagnetically. The iron(II) atoms are in the high spin state and its magnetic behaviour indicates the occurrence of zero-f…

A Singular Noninterpenetrating Coordination Polymer with the Pt3O4 Structure Containing Naked [Na+]4 Units

The homoleptic low-spin complex [Fe(L)3]2+ where L is the bisbidentate ligand 1,10-phenanthroline-5,6-dione, coordinates Na+ ions via exo-oriented dione groups defining a three-dimensional cationic network {[Fe(L)3]4Na3}11+}n with Pt3O4 topology. The large volume generated by the network is filled with 11 perchlorate ions, 7 "NaClO4" ionic pairs, and 9 H2O molecules. Singular [Na+]4 units, in which the Na+ ions are practically uncoordinated, are formed.

Thermal and light induced polymorphism in iron(II) spin crossover compounds.

The spin crossover complexes {Fe[H2B(pz)2]2L} ([H2B(pz)2]2 = dihydrobis(pyrazolyl)borate, L = 2,2'-bipyridine (1), bipy and 1,10-phenanthroline, phen (2)) undergo both thermal and light induced spin crossover, but the structure of the low spin and light induced high spin states for 2 are different from that of the thermally induced high spin state and from those of 1. Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

Titelbild: One Shot Laser Pulse Induced Reversible Spin Transition in the Spin-Crossover Complex [Fe(C4H4N2){Pt(CN)4}] at Room Temperature (Angew. Chem. 26/2005)

Supramolecular isomerism in spin crossover networks with aurophilic interactions

Assembly of FeII, 3-cyanopyridine and [Au(CN)2]– affords, in one-pot reaction, three coordination polymers that represent a genuine example of supramolecular isomerism with strong influence in the spin crossover regime of the FeII ions. Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

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

Cover Picture: One Shot Laser Pulse Induced Reversible Spin Transition in the Spin-Crossover Complex [Fe(C4H4N2){Pt(CN)4}] at Room Temperature (Angew. Chem. Int. Ed. 26/2005)

Cooperative Thermal and Optical Switching of Spin States in a New Two-Dimensional Coordination Polymer

{Fe(pmd)2[Cu(CN)2]2} (pmd = pyrimidine) displays a rigid two-dimensional structure and undergoes thermal- and optical-driven spin crossover behaviour; cooperative elastic coupling between iron(II) ions in the framework induces thermal hysteresis in the HS↔LS conversion and sigmoidal HS→LS relaxation of the photo-induced HS state at low temperatures. Niel, Virginie, Virginie.Niel@uv.es ; Galet Domingo, Ana Guadalupe, Ana.Galet@uv.es ; Gaspar Pedros, Ana Belen, Ana.B.Gaspar@uv.es ; Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

Coordination polymers undergoing spin crossover and reversible ligand exchange in the solid

Here we report the synthesis and characterisation of a polymer made up of a system of parallel 2-D grids of Fe(II) ions linked by [Au(CN)2]– bridges and its transformation into a new system of three interpenetrated 3-D coordination open frameworks with the NbO topology. Reversibility of this crystal-to-crystal transformation is evidenced by X-ray crystallographic data and from their spin crossover properties. Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

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)

Synthesis and X-Ray Single Crystal Structure of Two New Copper Complexes with the Redox Active Ligand 1,10-Phenanthroline-5,6-dione

The synthesis and the crystal structures of the complexes [Cu(LI)2](ClO4) (1) and [Cu(LI)(CH3CN)2(ClO4)2] (2) are reported. 1 crystallizes in the monoclinic space group C2/c with the unit cell dimensions a = 13.169(4), b = 12.289(3), c = 14.732(3) A, β = 109.03(2)° and Z = 4. Copper(I) is coordinated to four N atoms of the two 1,10-Phenanthroline-5,6-dione (LI) ligands with a two-fold axis passing between the ligands. The copper(II) compound 2 crystallizes in the orthorhombic space group Pbn21 with unit cell dimensions of a = 7.498(5), b = 23.492(7), c = 12.363(4) A and Z = 4. Copper(II) coordination can be described as a distorted octahedron with the N donor atoms of one LI ligand and of t…

One Shot Laser Pulse Induced Reversible Spin Transition in the Spin-Crossover Complex [Fe(C4H4N2){Pt(CN)4}] at Room Temperature

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…

Crystalline-state reaction with allosteric effect in spin-crossover, interpenetrated networks with magnetic and optical bistability.

A net change: A fully reversible ligand substitution involving coordination/ uncoordination of gaseous water and pyrimidine induces the repetitive allosteric transformation of three interpenetrated nets into a single three-dimensional net. The transformation does not affect the crystallinity of the sample but alters significantly the spin-crossover transition; the compound shows magnetic and chromatic bistability (see picture).

Pressure Effect Studies on the 3D Spin Crossover System: {Fe(3CN-py)2[M(CN)2]2}·nH2O (n < 2/3, M = Ag(I), Au(I))

[EN] Pressure effect investigations on the magnetic behaviour of the 3D SCO polymers {Fe(3CN-py)2[Ag(CN)2]2} · 2/3H2O (1) and {Fe(3CN-py)2[Au(CN)2]2} · 2/3H2O (2) have been carried out in the range of 105 Pa to 0.7 GPa. Despite both compounds are isostructural their magnetic behaviour under applied hydrostatic pressures is very different. Strong nonlinearity in the Tc(P) vs. P plot has been observed for compound 1 a fact which contrasts with the almost linear dependence observed for each spin transition in 2. However, both compounds are extremely sensitive to the application of pressure as well as the Tc(P) vs. P plots denote.

Thermal- and photoinduced spin-state switching in an unprecedented three-dimensional bimetallic coordination polymer.

The compound {Fe(pmd)[Ag(CN)2][Ag2(CN)3]} (pmd=pyrimidine) was synthesized and characterized. Magnetic, calorimetric and single crystal visible spectroscopic studies demonstrate the occurrence of a two-step high-spin (HS) right arrow over left arrow low-spin (LS) transition. The critical temperatures are T(c1)=185 and T(c2)=148 K. Each step involves approximately 50 % of the iron centers, with the low-temperature step showing a hysteresis of 2.5 K. The enthalpy and entropy variations associated with the two steps are DeltaH(1)=3.6+/-0.4 kJ mol(-1) and DeltaS(1)=19.5+/-3 J K(-1) mol(-1); DeltaH(2)=4.8+/-0.4 kJ mol(-1) and DeltaS(2)=33.5+/-3 J K(-1) mol(-1). Photomagnetic and visible spectros…