Enhanced porosity in a new 3D Hofmann-like network exhibiting humidity sensitive cooperative spin transitions at room temperature

Bartual‐Murgui, Carlos; Ortega-Villar, Norma; Shepherd, Helena J.; Muñoz, M. Carmen; Salmon, Lionel; Molnár, Gábor; Bousseksou, Azzedine; Real, José Antonio

doi:10.1039/c0jm04387g

Cited by 95 publications

(65 citation statements)

References 24 publications

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“…More recently a drastic influence of the guest inclusion on T 1/2 and cooperativity has been reported for the 3D Hofmann-like SCO-PCPs {Fe(L)[M(CN) 4 ]}·G [L = pz [363,422–425]; azpy [382]; bpac (bis(4-pyridyl)acetylene) [426]; dpe ( trans isomer) [300] M(II) = Ni, Pd, Pt)]. This type of framework provides two guest interactive sites, one between the organic bridges (site A) and another between the four-coordinate M centers (site B) (Fig.…”

Section: Reviewmentioning

confidence: 99%

Spin state switching in iron coordination compounds

Gütlich¹,

Gaspar²,

Garcia³

2013

Beilstein J. Org. Chem.

661

608

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SummaryThe article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors as well as optical devices.The article begins with a brief description of the principle of molecular spin state switching using simple concepts of ligand field theory. Conditions to be fulfilled in order to observe spin crossover will be explained and general remarks regarding the chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of pressure are subjects of two separate sections. The major part of this account concentrates on selected spin crossover compounds of iron(II), with particular emphasis on the chemical and physical influences on the spin crossover behavior. The vast variety of compounds exhibiting this fascinating switching phenomenon encompasses mono-, oligo- and polynuclear iron(II) complexes and cages, polymeric 1D, 2D and 3D systems, nanomaterials, and polyfunctional materials that combine spin crossover with another physical or chemical property.

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Section: Reviewmentioning

confidence: 99%

Spin state switching in iron coordination compounds

Gütlich¹,

Gaspar²,

Garcia³

2013

Beilstein J. Org. Chem.

661

608

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“…In fact, the well-known relativistic effects for heavy atoms explain the higher electron affinity of Au with respect to Ag. [23] These systems include large aromatic molecules, such as naphthalene, anthracene, phenazine, or 2,4,6trichlorophenol. [13] Finally, an important aspect of this work concerned the synthesis of new porous SCO-CPs.…”

Section: {M I (Cn) 2 } 2 ] Coordination Polymers An Interesting Excementioning

confidence: 99%

[Fe(TPT)_2/3{M^I(CN)₂}₂]⋅nSolv (M^I=Ag, Au): New Bimetallic Porous Coordination Polymers with Spin‐Crossover Properties

Arcís-Castillo

Muñoz

Molnár

et al. 2013

Chemistry A European J

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Two new heterobimetallic porous coordination polymers with the formula [Fe(TPT)(2/3){M(I)(CN)2}2]⋅nSolv (TPT = [(2,4,6-tris(4-pyridyl)-1,3,5-triazine]; M(I) = Ag (nSolv = 0, 1 MeOH, 2 CH2Cl2), Au (nSolv = 0, 2CH2Cl2)) have been synthesized and their crystal structures were determined at 120 K and 293 K by single-crystal X-ray analysis. These structures crystallized in the trigonal R-3m space group. The Fe(II) ion resides at an inversion centre that defines a [FeN6] coordination core. Four dicyanometallate groups coordinate at the equatorial positions, whilst the axial positions are occupied by the TPT ligand. Each TPT ligand is centred in a ternary axis and bridges three crystallographically equivalent Fe(II) ions, whilst each dicyanometallate group bridges two crystallographically equivalent Fe(II) ions that define a 3D network with the topology of NbO. There are two such networks, which interpenetrate each other, thereby giving rise to large spaces in which very labile solvent molecules are included (CH2Cl2 or MeOH). Crystallographic analysis confirmed the reversible structural changes that were associated with the occurrence of spin-crossover behaviour at the Fe(II) ions, the most significant structural variation being the change in unit-cell volume (about 59 Å(3) per Fe(II) ion). The spin-crossover behaviour has been monitored by means of thermal dependence of the magnetic properties, Mössbauer spectroscopy, and calorimetry.

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“…Indeed, the bis(4‐pyridyl)acetylene (bpac) ligand is rigid and longer than azpy and pz and so it should improve both the cooperativity and the porosity of the corresponding PCP materials. In recent reports, we have described the structural and magnetic properties of the novel {Fe(bpac)[Pt(CN) 4 ]}3a and {Fe(bpac) 2 [Ag(CN) 2 ] 2 }10 compounds. Similarly to the previously reported 3D porous SCO coordination Hofmann polymers {Fe( L )[Pt(CN) 4 ]} ( L =pz,4b azpy9), the crystal of the Pt/bpac derivative belongs to the tetragonal P 4/ mmm space group.…”

Section: Introductionmentioning

confidence: 99%

Synergetic Effect of Host–Guest Chemistry and Spin Crossover in 3D Hofmann‐like Metal–Organic Frameworks [Fe(bpac)M(CN)₄] (M=Pt, Pd, Ni)

Bartual‐Murgui¹,

Salmon²,

Akou³

et al. 2011

Chemistry A European J

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118

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The synthesis and characterization of a series of three-dimensional (3D) Hofmann-like clathrate porous metal-organic framework (MOF) materials [Fe(bpac)M(CN)(4)] (M=Pt, Pd, and Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin-crossover behavior is reported. The rigid bpac ligand is longer than the previously used azopyridine and pyrazine and has been selected with the aim to improve both the spin-crossover properties and the porosity of the corresponding porous coordination polymers (PCPs). The 3D network is composed of successive {Fe[M(CN)(4)]}(n) planar layers bridged by the bis-monodentate bpac ligand linked in the apical positions of the iron center. The large void between the layers, which represents 41.7% of the unit cell, can accommodate solvent molecules or free bpac ligand. Different synthetic strategies were used to obtain a range of spin-crossover behaviors with hysteresis loops around room temperature; the samples were characterized by magnetic susceptibility, calorimetric, Mössbauer, and Raman measurements. The complete physical study reveals a clear relationship between the quantity of included bpac molecules and the completeness of the spin transition, thereby underlining the key role of the π-π stacking interactions operating between the host and guest bpac molecules within the network. Although the inclusion of the bpac molecules tends to increase the amount of active iron centers, no variation of the transition temperature was measured. We have also investigated the ability of the network to accommodate the inclusion of molecules other than water and bpac and studied the synergy between the host-guest interaction and the spin-crossover behavior. In fact, the clathration of various aromatic molecules revealed specific modifications of the transition temperature. Finally, the transition temperature and the completeness of the transition are related to the nature of the metal associated with the iron center (Ni, Pt, or Pd) and also to the nature and the amount of guest molecules in the lattice.

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Enhanced porosity in a new 3D Hofmann-like network exhibiting humidity sensitive cooperative spin transitions at room temperature

Cited by 95 publications

References 24 publications

Spin state switching in iron coordination compounds

Spin state switching in iron coordination compounds

[Fe(TPT)_2/3{M^I(CN)₂}₂]⋅nSolv (M^I=Ag, Au): New Bimetallic Porous Coordination Polymers with Spin‐Crossover Properties

Synergetic Effect of Host–Guest Chemistry and Spin Crossover in 3D Hofmann‐like Metal–Organic Frameworks [Fe(bpac)M(CN)₄] (M=Pt, Pd, Ni)

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Enhanced porosity in a new 3D Hofmann-like network exhibiting humidity sensitive cooperative spin transitions at room temperature

Cited by 95 publications

References 24 publications

Spin state switching in iron coordination compounds

Spin state switching in iron coordination compounds

[Fe(TPT)2/3{MI(CN)2}2]⋅nSolv (MI=Ag, Au): New Bimetallic Porous Coordination Polymers with Spin‐Crossover Properties

Synergetic Effect of Host–Guest Chemistry and Spin Crossover in 3D Hofmann‐like Metal–Organic Frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni)

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Product

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[Fe(TPT)_2/3{M^I(CN)₂}₂]⋅nSolv (M^I=Ag, Au): New Bimetallic Porous Coordination Polymers with Spin‐Crossover Properties

Synergetic Effect of Host–Guest Chemistry and Spin Crossover in 3D Hofmann‐like Metal–Organic Frameworks [Fe(bpac)M(CN)₄] (M=Pt, Pd, Ni)