Jean-Daniel Compain

Iron Polyoxometalate Single‐Molecule Magnets

Iron sandwich on a tungstate bun: Two new polyoxotungstates with paramagnetic iron(III) heteroatoms (see structure, W blue, Fe yellow, O red) possess S=15/2 and S=5 ground states. Both compounds are single-molecule magnets, and the hexairon species shows large hysteresis (see picture) and quantum tunneling effects at low temperature. Electrochemical studies indicate that these species are stable in solution for a wide range of pH values.

Magnetic Bistability of Individual Single-Molecule Magnets Grafted on Single-Wall Carbon Nanotubes†

A POM to remember: Hexanuclear Fe(III) polyoxometalate (POM) single-molecule magnets (see structure) can be noncovalently assembled on the surface of single-wall carbon nanotubes. Complementary characterization techniques (see TEM image and magnetic hysteresis loops) demonstrate the integrity and bistability of the individual molecules, which could be used to construct single-molecule memory devices.

Water Substitution on Iron Centers: from 0D to 1D Sandwich Type Polyoxotungstates

Four novel polyoxotungstates have been synthesized by reaction of the sandwich type compound [Fe (III) 4(H 2O) 10(B-beta-SbW 9O 33) 2] (6-) (noted Fe 4(H 2O) 10Sb 2W 18) with ethylenediamine (en) and/or oxalate (ox) ligands under various conditions. The one-dimensional (1D) compound [enH 2] 3[Fe (III) 4(H 2O) 8(SbW 9O 33) 2].20H 2O ( 1) is isolated at 130 degrees C and results from the elimination of two water molecules and the condensation of the polyoxotungstate precursor. The reaction of Fe 4(H 2O) 10Sb 2W 18 with oxalate ligands affords the molecular complex Na 14[Fe (III) 4(ox) 4(H 2O) 2(SbW 9O 33) 2].60H 2O ( 2) where two organic ligands substitute four water molecules, while the same reaction in the presence of en molecules at 130 degrees C leads to the formation of the functionalized 1D chain [enH 2] 7[Fe (III) 4(ox) 4(SbW 9O 33) 2].14H 2O ( 3) with protonated ethylenediamine counterions. Finally, at 160 degrees C a rearrangement of the Fe 4(H 2O) 10Sb 2W 18 polyoxotungstate is observed, and the sandwich type compound [enH 2] 5[Fe (II) 2Fe (II) 2(enH) 2(Fe (III)W 9O 34) 2].24H 2O ( 4) crystallizes. In 4, the heteroelement is a Fe (III) ion, and the water molecules on the two outer Fe (II) centers are bound to pendant monoprotonated en ligands. The four compounds have been characterized by IR spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. A detailed study of the magnetic properties of the mixed-valent hexanuclear iron complex in 4 shows evidence of an S = 5 ground-state because of spin frustration effects. A quantification of the electronic parameters characterizing the ground state ( D = +1.12 cm (-1), E/ D = 0.15) confirms that polyoxotungstate ligands induce large magnetic anisotropy.

Second-Order Nonlinear Optical Properties of Polyoxometalate Salts of a Chiral Stilbazolium Derivative

The synthesis of nonlinear optical (NLO) active salts with stilbazolium derivatives and polyoxometalate (POM) counterions has been investigated. With known nonchiral stilbazolium derivatives, such as MOMS(+), compounds with centrosymmetric structures have been isolated, like for instance the centrosymmetric salt (MOMS)(4)[Mo(8)O(26)] (1), synthesized under hydrothermal conditions. A new chiral derivative of the known DAMS(+) molecules, named here CHIDAMS(+), has therefore been synthesized in order to force the crystallization of the hybrid ionic salts in noncentrosymmetric space groups. The CHIDAMS(+) cation has been crystallized under two polymorphic PF(6)(-) salts, (CHIDAMS)PF(6) (2a and 2b), and its reactivity with various POMs has been investigated. The ionic salt (CHIDAMS)(2)[Mo(5)O(13)(OEt)(4)(NO){Na(H(2)O)(0.5)(DMF)(0.5)}] (4) crystallizes in the noncentrosymmetric P2(1) group, but the push-pull axis of the CHIDAMS(+) cations adopts a quasi-antiparallel alignment. The ionic salt (CHIDAMS)(3)[PW(12)O(40)].2DMF (5) associating three CHIDAMS(+) cations and a PW(12)O(40)(3-) Keggin anion crystallizes also in the P2(1) space group, but the disposition of the cations in the solid state is far more favorable. Diffuse reflectance experiments have evidenced a charge transfer between the organic and inorganic components in 5, and Kurtz-Perry experiments show that this salt exhibits a second harmonic generation efficiency more than 10 times higher than those of the PF(6)(-) salts 2a and 2b, the hybrid salt 4, and all of the other NLO active POM molecular materials reported in the literature.

Structural, Magnetic, EPR, and Electrochemical Characterizations of a Spin-Frustrated Trinuclear CrIII Polyoxometalate and Study of Its Reactivity with Lanthanum Cations

The asymmetric Cr(III) polyoxometalate complex Cs(10)[(gamma-SiW(10)O(36))(2)(Cr(OH)(H(2)O))(3)] x 17 H(2)O (1) has been synthesized in water under atmospheric pressure from the trinuclear precursor [Cr(3)(CH(3)COO)(7)(OH)(2)] and the divacant ligand [gamma-SiW(10)O(36)](8-). Complex 1 is built up of two [gamma-SiW(10)O(36)](8-) Keggin units sandwiching a trinuclear {(Cr(III)(OH)(H(2)O))(3)} fragment where the paramagnetic centers are bridged by three mu-OH ligands forming a nearly isosceles triangle. The magnetic properties of this spin-frustrated system have thus been interpreted considering a 2-J Hamiltonian showing that the Cr(III) ions are antiferromagnetically coupled and that 1 possesses an S = 3/2 ground state with an S = 1/2 first excited state located at 11 cm(-1). These results have been confirmed by EPR spectroscopy measurements (Q-band), which have also enabled the quantification of the electronic parameters characterizing the quadruplet spin ground state. The magnitude of the magnetic exchange interactions and the nature of the ground state are discussed in light of previously reported isosceles triangular S = 3/2 clusters. UV-visible and electrochemical studies have shown that 1 is stable in aqueous media in a 1-7 pH range. This stability is chemically confirmed by the study of the reactivity of 1 with La(III) cations, which has allowed the isolation of the Cs(4)[(gamma-SiW(10)O(36))(2)(Cr(OH)(H(2)O))(3)(La(H(2)O)(7))(2)] x 20 H(2)O compound (2). Indeed, during the synthetic process of this 3d-4f system, the integrity of the [(gamma-SiW(10)O(36))(2)(Cr(OH)(H(2)O))(3)](10-) building unit constituting 1 is maintained despite the high oxophilic character of the La(III) ions. The single crystal X-ray diffraction study of 2 has revealed that in the solid state the rare earth cations connect these subunits, affording a 3d-4f double-chain monodimensional system.

Hexa- and Dodecanuclear Polyoxomolybdate Cyclic Compounds: Application toward the Facile Synthesis of Nanoparticles and Film Electrodeposition

Two new compounds based on O(3)PCH(2)PO(3)(4-) ligands and {Mo(V)(2)O(4)} dimeric units have been synthesized and structurally characterized. The dodecanuclear Mo(V) polyoxomolybdate species in (NH(4))(18)[(Mo(V)(2)O(4))(6)(OH)(6)(O(3)PCH(2)PO(3))(6)] x 33 H(2)O (1) is a cyclohexane-like ring in a chair conformation with pseudo S(6) symmetry. In the solid state, the wheels align side by side, thus delimiting large rectangular voids. The hexanuclear anion in Na(8)[(Mo(V)(2)O(4))(3)(O(3)PCH(2)PO(3))(3)(CH(3)AsO(3))] x 19 H(2)O (2) has a triangular framework and encapsulates a methylarsenato ligand. (31)P NMR spectroscopic analysis revealed the stability of 2 in various aqueous media, whereas the stability of 1 depends on the nature of the cations present in solution. It has been evidenced that the transformation of 1 into 2 occurs in the presence of CH(3)AsO(3)(2-) ions. This behavior shows that 1 can be used as a new precursor for the synthesis of Mo(V)/diphosphonate systems. The two complexes were very efficient both as reductants of Pt and Pd metallic salts and as capping agents for the resulting Pt(0) and Pd(0) nanoparticles. The size of the obtained nanoparticles depends both on the nature of the polyoxometalate (POM; i.e., 1 or 2) and on the [metallic salt]/[POM] ratio. In all cases, X-ray photoelectron spectroscopy (XPS) measurements have revealed the presence of Mo(VI) species that stabilize the nanoparticles and the absence of Mo(V) moieties. Diffuse-reflectance FTIR spectra of the Pt nanoparticles show that the capping Mo(VI) POMs are identical for both systems and contain the diphosphonato ligand. The colloidal solutions do not show any precipitate and the nanoparticles remain well-dispersed for several months. The electrochemical reduction of Mo(V) species was studied for 2. Cyclic voltammetry alone and electrochemical quartz crystal microbalance coupled with cyclic voltammetry show the deposition of a film on the electrode surface during this reduction.

A polyoxometalate-cyanometalate multilayered coordination network.

The reaction of the ε-Keggin polyoxometalate (POM) [PMo(12)O(36)(OH)(4){La(H(2)O)(4)}(4)](5+) with Fe(II)(CN)(6)(4-) under typical bench conditions at room temperature and ambient pressure has afforded the novel [ε-PMo(12)O(37)(OH)(3){La(H(2)O)(5)(Fe(CN)(6))(0.25)}(4)] network, which exhibits a three-dimensional multilayered structure. The compound has been fully characterized by synchrotron-radiation X-ray crystallography, IR spectroscopy, elemental analysis, and thermogravimetric analysis. This coordination network constitutes the first example of a cyanometalate bonded to a POM unit.