Design of oxide nanoparticles by aqueous chemistry

The elaboration of nanoparticles designed for technological applications in various fields such as catalysis, optics, magnetism, electronics… needs the strict control of their characteristics, especially chemical composition, crystalline structure, size, and shape. These characteristics bring the physical properties (color, magnetism, band gap…) of the material, and also the surface to volume ratio of particles which is of high importance when they are used as a chemically active or reactive support, in catalysis for instance. The nanoparticles may have also to be surface functionalized by various species, and/or dispersed in aqueous or non aqueous media. We will show that the aqueous chemistry of metal cations is a very versatile and attractive way for the design of oxide nanomaterials, allowing the control of size, shape, and crystalline structure for polymorphic materials. Aqueous surface chemistry, including adsorption of various species, may be used to modify the morphology of nanoparticles. In some cases, redox processes can be involved to control the morphology of nanoparticles. Technologically important nanomaterials such as titania, alumina, and iron oxides are studied.     

A variety of spin-crossover behaviors depending on the counter anion: two-dimensional complexes constructed by NH...Cl- hydrogen bonds, [FeIIH3LMe]Cl.X (X = PF6 -, AsF6 -, SbF6 -, CF3SO3 -; H3L(Me) = Tris[2-{[(2-methylimidazol-4-yl)methylidene]amino}ethyl]amine)

A family of spin-crossover (SC) complexes, [Fe(II)H(3)L(Me)]Cl.X (X(-) = PF(6) (-), AsF(6) (-), SbF(6) (-), CF(3)SO(3) (-)), 1-4, has been synthesized, in which H(3)L(Me) denotes the hexadentate N(6) tripod-like ligand tris[2-{[(2-methylimidazol-4-yl)methylidene]amino}ethyl]amine, containing three imidazole groups, with a view to establishing the effect of the counter anion on the SC behavior. These complexes have been found to crystallize in the same monoclinic crystal system with similar cell dimensions. The general crystal structure consists of a two-dimensional (2D) extended network constructed by NH...Cl- hydrogen bonds between Cl- and the imidazole NH groups of three neighboring [Fe(II)H(3)L(Me)]2+ ions, while the anion X exists as an isolated counter anion and occupies the space between the 2D sheets. Magnetic susceptibilities and M?ssbauer spectra have revealed a variety of SC behaviors depending on the counter anion, including a one-step HS<==>(HS + LS)/2 (1, X = PF(6) (-)), a two-step HS<==>(HS + LS)/2<==>LS with a slow thermal relaxation (2, X = AsF(6) (-)), a gradual one-step HS<==>LS (3, X = SbF(6) (-)), and a steep one-step HS<==>LS with hysteresis (4, X = CF(3)SO(3) (-)). The complexes assume the space group P2(1)/n in the HS state, P2(1) in the HS + LS state, and P2(1)/n in the LS state. The Fe-N bond lengths and the N-Fe-N bond angles are indicative of the HS, HS + LS, and LS states. The molecular volumes, V, of the counter anions have been evaluated by quantum-chemical calculations as follows: 53.4 A(3) (BF(4) (-)), 54.4 A(3) (ClO(4) (-)), 73.0 A(3) (PF(6) (-)), 78.5 A(3) (AsF(6) (-)), 88.7 A(3) (SbF(6) (-)), and 86.9 A(3) (CF(3)SO(3) (-)). The size and shape of the counter anion affects the flexible 2D network structure constructed by the hydrogen bonds, leading to modifications of the SC behavior. These estimated relative sizes of the counter anions correlate well with the observed SC behaviors.     

Monomeric iron(II) hydroxo and iron(III) dihydroxo complexes stabilized by intermolecular hydrogen bonding

Using the multidentate ligand bis(N-methylimidazol-2-yl)-3-methylthiopropanol (L), the mononuclear iron(II) hydroxo and iron(III) dihydroxo complexes [Fe(II)(L)2(OH)](BF4) (1) and [Fe(III)(L)2(OH)2](BF4) (2) have been synthesized and characterized by X-ray diffraction and spectroscopic methods. The X-ray data suggest that the remarkable stability of the Fe-OH bond(s) in both compounds results from intermolecular hydrogen-bonding interactions between the hydroxo ligand(s) and the tertiary hydroxyl of the L ligands, which prevent further intermolecular reactions.     

AB initio study of the regular polyhedral molecules N4, P4, As4, N8, P8 and As8

Ab initio pseudopotential SCF calculations were performed on tetrahedral X₄ molecules using double-zeta basis sets with and without d functions. The inclusion of d orbitals shortens the bond lengths, stabilizes the X₄ structures and intensifies the electron density inside the tetrahedron. The cubic X₈ molecules, calculated without d AOs, are not predicted to be more stable than 2X₄. Repulsions between parallel bonds in X₈ may compensate the lack of ring strain.     

High-spin to low-spin relaxation kinetics in the [Fe(TRIM)2]Cl2 complex

A quasi-quantitative photo-induced low-spin (LS)-->high-spin (HS) conversion of FeII ions has been observed in the [Fe(TRIM)2]Cl2 complex by irradiating the sample with blue light (488 nm) at 10 K. The time dependence of the HS-->LS relaxation has been studied between 10 K and 44 K by means of magnetic susceptibility measurements. These relaxation curves could be satisfactorily fitted by mono-exponential decays including tunnelling effect except for temperatures below 30 K. The introduction of a distribution of vibrational frequencies into this model improved significantly the fits in the low-temperature range and gave a good agreement with the experimental data in the whole temperature range suggesting a multi-rate relaxation process in this complex.     

Synthese et reactivite d''organometalliques perfluores. VII [1] reactivite comparee de derives perfluoroalkyles satures et insatures de l''etain et du mercure vis-a-vis d''electrophiles.

The reactivity of some derivatives of perfluorooctenyl-tin, perfluorooctenyl-mercury and perfluorooctyl-mercury towards protic acids, especially hydrogen chloride, is studied.

The easy cleavage of the tin - sp² carbon bond is painted out, and used to study possibilities of transferring the perfluorooctenyl radical on mercury, upon reaction with mercuric salts.

The mercury-perfluoroalkyl radical bond is shown to be, on the contrary, very resistant to an electrophilic attack.

These results are compared to those concerning the hydrocarbon analogs, and an interpretation, relied to the electronic density on the carbon atom bound to the metallic atom, is given.     

Photocyclisation d'hydroxyalkyl glycosides en orthoesters glycosidiques

A free-radical cyclization process makes glycosidic orthoester structures readily available in a one-pot procedure.     

Structures de deux β-énaminoesters cycliques: l'α-(tétrahydropyrrolidinylidéne-2) acétate d'éthyle et l'α-(hexahydroazepinylidéne-2) acétate d'éthyle

The structure of ethyl α-(tetrahydro-2-pyrrolidinylidene) and α-(hexahydro-2-azepinylidene) acetates has been determined from the X-ray crystallographic analysis. The results show that, in a solid state, these compounds exist as β-enaminoesters which have a Z configuration. They also show the presence of intra and intermolecular hydrogen bonding.     

Reduced number of steps for the synthesis of dense and highly functionalized dendrimers

A series of densely functionalized dendrimers is synthesized using two branched monomers of type AB₂ and CD₂, in which the A function (NH₂) reacts with D (CHO) and the B function (Cl) reacts with C (OH). The reaction has been carried out up to the fourth generation possessing 96 end groups and has been obtained in only four steps.     

Photomagnetic properties of an iron(II) low-spin complex with an unusually long-lived metastable LIESST state

A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long-lived metastable HS state. This underlines the preponderant role of the inner coordination sphere for stabilizing the lifetime of the photoinduced HS state.