Corine Mathonière

Photomagnetism in Clusters and Extended Molecule-Based Magnets

Photomagnetism in molecular systems is a new development in molecular magnetism. It traces back to 1982 and 1984 when a transient effect and then the light-induced excited-spin-state-trapping effect was discovered in spin-crossover complexes. The present contribution gives a definition of the phenomenon, a process that changes the magnetism of a (molecular) system after absorption of a photon. It is limited to the discussion of photomagnetism based on metal-metal electron transfer in clusters and extended molecule-based magnets. The paper is organized around the main pairs of spin bearers, which allowed us to evidence and to study the phenomenon: Cu-Mo, Co-Fe, and Co-W. For each metallic pair, we report and discuss the conditions of appearance of the effect and its characteristics, both in extended structures and in molecular units: structure, spectroscopy, magnetism, thermodynamics and kinetics, and applications. We conclude with some brief prospects. The field is in rapid expansion. We are convinced that the interaction of photons with magnetized matter, to provide original magnetic properties, will meet more and more interest in the future.

Reversible Thermally and Photoinduced Electron Transfer in a Cyano‐Bridged {Fe2Co2} Square Complex

Flip to be square: Structural, spectroscopic, magnetic, and photomagnetic studies conclusively demonstrate that a tetranuclear cyanometalate {Fe2Co2} complex undergoes reversible thermally and light-induced changes in optical and magnetic properties. This instability is induced by an intramolecular electron transfer, as oberved in three-dimensional Co/Fe Prussian blue compounds (see picture).

Photoinduced Single-Molecule Magnet Properties in a Four-Coordinate Iron(II) Spin Crossover Complex

The four-coordinate Fe(II) complex, PhB(MesIm)3Fe-N═PPh3 (1) has been previously reported to undergo a thermal spin-crossover (SCO) between high-spin (HS, S = 2) and low-spin (LS, S = 0) states. This complex is photoactive below 20 K, undergoing a photoinduced LS to HS spin state change, as determined by optical reflectivity and photomagnetic measurements. With continuous white light irradiation, 1 displays slow relaxation of the magnetization, i.e. single-molecule magnet (SMM) properties, at temperatures below 5 K. This complex provides a structural template for the design of new photoinduced mononuclear SMMs based on the SCO phenomenon.

Tristability in a Light-Actuated Single-Molecule Magnet

Molecules exhibiting bistability have been proposed as elementary binary units (bits) for information storage, potentially enabling fast and efficient computing. In particular, transition metal complexes can display magnetic bistability via either spin-crossover or single-molecule magnet behavior. We now show that the octahedral iron(II) complexes in the molecular salt [Fe(1-propyltetrazole)6](BF4)2, when placed in its high-symmetry form, can combine both types of behavior. Light irradiation under an applied magnetic field enables fully reversible switching between an S = 0 state and an S = 2 state with either up (M(S) = +2) or down (M(S) = -2) polarities. The resulting tristability suggests the possibility of using molecules for ternary information storage in direct analogy to current binary systems that employ magnetic switching and the magneto-optical Kerr effect as write and read mechanisms.

Crystal structure and magnetic properties of the layer ferrimagnet N(n-C5H11)4MnIIFeIII(C2O4)3

The crystal structure and magnetic properties of the molecular-based ferrimagnet N(n-C5H11)4MnIIFeIII(C2O4)3 have been determined. The compound is orthorhombic, space group C2221, a= 9.707(3), b= 16.140(3), c= 19.883(7)A(120 K), Z= 4[R 0.047 for I > 2σ(I)]. The structure consists of hexagonal layers of alternating MnII and FeIII bridged by C2O42–, separated by layers containing only N(n-C5H11)4+ with the alkyl chains extended, though with the terminal bonds twisted towards the gauche conformation. The terminal CH3 are embedded in the hexagonal pockets formed by three C2O42–. Since both metal ions have 3d5 configuration with 6A1 ground states the magnetic properties in the paramagnetic region mimic those of a two-dimensional antiferromagnet. Below TN= 27 K an uncompensated moment estimated as 8.78 × 10–5µB atom–1 arises, the direction of which was identified as parallel to the c axis by single-crystal magnetization measurements.

Hepta/octa cyanomolybdates with Fe2+: influence of the valence state of Mo on the magnetic behavior

Two FeII-based molybdenum polycyanides, Fe2[MoIII(CN)7]·8H2O and [Fe2(H2O)4][MoIV(CN)8]·4H2O, have been synthesized. The compound [Fe2(H2O)4][MoIV(CN)8]·4H2O crystallizes in the tetragonal system, space group I422. There are two molybdenum sites in a distorted square antiprism arrangement, each site being surrounded by eight CN–Fe linkages. The distorted octahedral iron site is formed by four NC–Mo linkages and two water molecules in apical positions. The structure is three-dimensional and highly symmetrical. The magnetic characteristics of these two compounds were compared. Fe2[MoIII(CN)7]·8H2O orders below 65 K as a ferrimagnet, but [Fe2(H2O)4][MoIV(CN)8]·4H2O shows no evidence of long-range magnetic order, obviously due to the contribution of the diamagnetic MoIV which suppresses the propagation of magnetic interaction between adjacent iron(II) ions through CN bridges. The results are discussed in the light of the single-crystal structural features of [Fe2(H2O)4][MoIV(CN)8]·4H2O.

Photomagnetic nanorods of the Mo(CN)8Cu2 coordination network

Nanorods of the photomagnetic coordination network Mo(CN)8Cu2 coated with polyvinylpyrrolidone were prepared and exhibit an enhanced effect upon irradiation when compared to the bulk.

Metal-to-metal electron transfer in Co/Fe Prussian Blue molecular analogues: the ultimate miniaturization.

Co/Fe Prussian Blue analogues are known to display both thermally and light induced electron transfer attributed to the switching between diamagnetic {Fe(II)LS(μ-CN)Co(III)LS} and paramagnetic {Fe(III)LS(μ-CN)Co(II)HS} pairs (LS = low spin; HS = high spin). In this work, a dinuclear cyanido-bridged Co/Fe complex, the smallest {Fe(μ-CN)Co} moiety at the origin of the remarkable physical properties of these systems, has been designed by a rational building-block approach. Combined structural, spectroscopic, magnetic and photomagnetic studies reveal that a metal-to-metal electron transfer that can be triggered in solid state by light, temperature and solvent contents, is observed for the first time in a dinuclear complex.

New μ4-Oxido-Bridged Copper Benzoate Quasi-Tetrahedron and Bis-μ3-Hydroxido-Bridged Copper Azide and Copper Thiocyanate Stepped Cubanes: Core Conversion, Structural Diversity, and Magnetic Properties

[Cu(2)(mu(4)-O)Cu(2)] and [Cu(2)(mu(3)-OH)(2)Cu(2)] geometrical arrangements are found in a new family of tetranuclear complexes: [Cu(4)(mu(4)-O)(mu-bip)(2)(mu-O(2)CPh)(4)].0.5CH(2)Cl(2) (1.0.5CH(2)Cl(2)), [Cu(4)(mu(3)-OH)(2)(mu-bip)(2)(N(3))(4)] (2), and [Cu(4)(mu(3)-OH)(2)(mu-bip)(2)(NCS)(4)(DMF)(2)] (3.2DMF) [Hbip = 2,6-bis(benzyliminomethyl)-4-methylphenol; DMF = dimethylformamide]. These complexes have been characterized by X-ray crystallography, and their magnetic properties have been studied. Complex 1 reacts with azide and thiocyanate anions, leading to 2 and 3 with a change of the [Cu(4)(mu(4)-O)] core into [Cu(4)(mu(3)-OH)(2)] units. These compounds are new examples of [Cu(4)] complexes where Cu(II) ions are connected by two types of water-derived ligands: oxide and hydroxide. Formation of these [Cu(4)] complexes can be controlled by changing the bridging ligands, which allows an effective tuning of the self-assembly. The study of the magnetic properties reveals that these complexes exhibit strong intramolecular antiferromagnetic interactions to yield a S(T) = 0 ground state. For the three complexes, the temperature dependence of the magnetic susceptibility was fitted using a model with two isolated S = 1/2 dimers based on the H = -2J{S(Cu,1).S(Cu,2)} spin Hamiltonian with J/k(B) = -289 K for 1; J/k(B) = -464 and -405 K for 2 and 3, respectively (where J is the exchange constant through the oxido-phenoxido or hydroxido-phenoxido bridges, respectively).

Slow magnetic relaxation and charge-transfer in cyano-bridged coordination clusters incorporating [Re(CN)(7)](3-/4-).

Treatment of the cyanometalate building unit [Re(CN)(7)](3-) with [(PY5Me(2))M(MeCN)](2+) (M = Co, Ni, Cu) affords a series of pentanuclear clusters of formulas [(PY5Me(2))(4)M(4)Re(CN)(7)](5+) (M = Co, Ni, Cu) and [(PY5Me(2))(4)Cu(4)Re(CN)(7)](4+). Single crystal X-ray diffraction analyses of the clusters reveal a star-like structure in which four [(PY5Me(2))M](2+) moieties are linked to a central [Re(CN)(7)](3-) unit via bridging cyanide ligands. An intramolecular Co(II) → Re(IV) charge-transfer accompanies the formation of the Co(II)(4)Re(IV) cluster, giving a Co(II)(3)Co(III)Re(III) species. Spectroelectrochemical methods and irradiation experiments are used to characterize the metal-metal charge-transfer bands of this compound. A rhenium-based thermally induced one-electron reduction is observed for the Cu(II)(4)Re(IV) cluster to give a Cu(II)(4)Re(III) complex; however, this reduction may be forestalled at low temperature. Finally, magnetic measurements reveal intracluster ferromagnetic exchange coupling, strong uniaxial magnetic anisotropy, and slow magnetic relaxation in the Ni(II)(4)Re(IV) and Cu(II)(4)Re(IV) clusters.