Microwave-Assisted and Metal-Induced Crystallization: A Rapid and Low Temperature Combination.

Here, we present a new crystallization process which, by combining microwaves and metal-induced devitrification, reduces both the time and the temperature of crystallization compared to other known methods. Titania crystallization initiates at a temperature as low as 125 °C within a few minutes of microwave radiation. Several cations induce this low-temperature crystallization, namely, Mn2+, Co2+, Ni2+, Al3+, Cu2+ and Zn2+. The crystallization mechanism is probed with electron microscopy, elemental mapping, single-particle inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, Auger electron spectroscopy, and scanning Auger mapping. These techniques show that the metal ion migration through the vitreous titania under microwave radiation occurs prior to crystallization. The crystalline particles are suspended in solution at the end of the treatment, avoiding particle aggregation and sintering. The crystalline suspensions are thus ready for processing into a material or employment in any other application. This combination of microwaves and metal-induced crystallization is applied here to TiO2, but we are investigating its application to other materials as an ecofriendly crystallization method.

Effect of solvent on silicon nanoparticle formation and size: a mechanistic study.

Silicon has emerged as the most desirable material for optical dielectric metamaterials, however chemists struggle to obtain the required silicon nanoparticle dimensions. Here the average diameter of silicon nanoparticles is varied between 3 and 15 nm by changing the reaction solvent. Electrochemistry and NMR elucidate the role of solvent on the synthetic mechanism. Surprisingly the solvent does not stabilize the nanoparticles and there is no trend associated with chain length or open-chain versus cyclical solvent molecules. The solvent's main role is to stabilize the by-products, which prolongs the reaction lifetime.

A new compound in the BEDT-TTF family [BEDT-TTF = bis-(ethyl-enedi-thio)-tetra-thia-fulvalene] with a tetra-thio-cyanato-cuprate(II) anion, (BEDT-TTF)4[Cu(NCS)4].

A new phase combining BEDT-TTF and [Cu(NCS)4]2- as the counter-anion, namely bis-[bis(ethyl-enedi-thio)-tetra-thia-fulvalenium] tetra-thio-cyanato-cuprate(II) bis-[bis(ethyl-ene-di-thio)-tetra-thia-fulvalene], (C10H8S8)2[Cu(NCS)4]·2C10H8S8 or (BEDT-TTF)4[Cu(NCS)4] was obtained during a galvanostatic electrocrystallization process. As previously observed with BEDT-TTF-based compounds with oxalatometallate anions, the BEDT-TTF mol-ecules in (BEDT-TTF)4[Cu(NCS)4] exhibit the so-called pseudo-κ arrangement, with two BEDT-TTF mol-ecules being positively charged and two electronically neutral. The bond lengths and angles in the two unique BEDT-TTF mol-ecules differ slightly. The crystal structure consists of layers of BEDT-TTF mol-ecules extending parallel to (001). The width of this layer corresponds to the length of the a axis [16.9036 (17) Å]. The BEDT-TTF layers are separated by layers of centrosymmetric square-planar [Cu(NCS)4]2- dianions.

Concerted Growth and Ordering of Cobalt Nanorod Arrays as Revealed by Tandem in Situ SAXS-XAS Studies.

The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray absorption spectroscopy-small-angle X-ray scattering (XAS-SAXS). The supercrystals were obtained by reducing a Co(II) precursor under H2 in the presence of a long-chain amine and a long-chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom-by-atom anisotropic growth, and a slower oriented attachment process that continues well after cobalt reduction is complete. Smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized superlattices, which can be regarded as mesocrystals.

The spontaneous formation and plasmonic properties of ultrathin gold-silver nanorods and nanowires stabilized in oleic acid.

Ultrathin Au-Ag alloy nanorods and nanowires of different lengths and ca. 1.9 nm diameter are prepared through a low-temperature decomposition of the precursor [Au2Ag2(C6F5)4(OEt2)2]n in oleic acid. This nanostructure formation has been studied through TEM, HRTEM, EDS, HS-SPME-GC-MS and (19)F NMR spectroscopy. The UNRs and UNWs display a length-dependent broad band in the mid-IR region that is related to the longitudinal mode of the surface plasmon resonance of the ultrathin nanostructures.

Oriented Metallic Nano-Objects on Crystalline Surfaces by Solution Epitaxial Growth.

Chemical methods offer the possibility to synthesize a large panel of nanostructures of various materials with promising properties. One of the main limitations to a mass market development of nanostructure based devices is the integration at a moderate cost of nano-objects into smart architectures. Here we develop a general approach by adapting the seed-mediated solution phase synthesis of nanocrystals in order to directly grow them on crystalline thin films. Using a Co precursor, single-crystalline Co nanowires are directly grown on metallic films and present different spatial orientations depending on the crystalline symmetry of the film used as a 2D seed for Co nucleation. Using films exposing 6-fold symmetry surfaces such as Pt(111), Au(111), and Co(0001), the Co heterogeneous nucleation and epitaxial growth leads to vertical nanowires self-organized in dense and large scale arrays. On the other hand, using films presenting 4-fold symmetry surfaces such as Pt(001) and Cu(001), the Co growth leads to slanted wires in discrete directions. The generality of the concept is demonstrated with the use of a Fe precursor which results in Fe nanostructures on metallic films with different growth orientations which depend on the 6-fold/4-fold symmetry of the film. This approach of solution epitaxial growth combines the advantages of chemistry in solution in producing shape-controlled and monodisperse metallic nanocrystals, and of seeded growth on an ad hoc metallic film that efficiently controls orientation through epitaxy. It opens attractive opportunities for the integration of nanocrystals in planar devices.

Air- and water-resistant noble metal coated ferromagnetic cobalt nanorods.

Cobalt nanorods possess ideal magnetic properties for applications requiring magnetically hard nanoparticles. However, their exploitation is undermined by their sensitivity toward oxygen and water, which deteriorates their magnetic properties. The development of a continuous metal shell inert to oxidation could render them stable, opening perspectives not only for already identified applications but also for uses in which contact with air and/or aqueous media is inevitable. However, the direct growth of a conformal noble metal shell on magnetic metals is a challenge. Here, we show that prior treatment of Co nanorods with a tin coordination compound is the crucial step that enables the subsequent growth of a continuous noble metal shell on their surface, rendering them air- and water-resistant, while conserving the monocrystallity, metallicity and the magnetic properties of the Co core. Thus, the as-synthesized core-shell ferromagnetic nanorods combine high magnetization and strong uniaxial magnetic anisotropy, even after exposure to air and water, and hold promise for successful implementation in in vitro biodiagnostics requiring probes of high magnetization and anisotropic shape.

Solution epitaxial growth of cobalt nanowires on crystalline substrates for data storage densities beyond 1 Tbit/in2.

The implementation of nano-objects in numerous emerging applications often demands their integration in macroscopic devices. Here we present the bottom-up epitaxial solution growth of high-density arrays of vertical 5 nm diameter single-crystalline metallic cobalt nanowires on wafer-scale crystalline metal surfaces. The nanowires form regular hexagonal arrays on unpatterned metallic films. These hybrid heterostructures present an important perpendicular magnetic anisotropy and pave the way to a high density magnetic recording device, with capacities above 10 Terabits/in(2). This method bypasses the need of assembling and orientating free colloidal nanocrystals on surfaces. Its generalization to other materials opens new perspectives toward many applications.

Liquid crystalline polymer-Co nanorod hybrids: structural analysis and response to a magnetic field.

This work deals with the structural analysis of side-chain liquid crystalline polysiloxanes, doped with magnetic cobalt nanorods, and their orientational properties under a magnetic field. These new materials exhibit the original combination of orientational behavior and ferromagnetic properties at room temperature. Here we show that, within the liquid crystal polymer matrix, the cobalt nanorods self-assemble in bundles made of nanorod rows packed in a 2-dimensional hexagonal lattice. This structure accounts for the magnetic properties of the composites. The magnetic and orientational properties are discussed with respect to the nature of the polymer matrix.

Organometallic precursors of nano-objects, a critical view.

The synthesis of nanoparticles has experienced a huge development over the past 20 years. However, this development has remained relatively limited to a few classes of nanomaterials such as iron oxides, semi-conducting oxides, plasmonic nanoparticles (essentially Au) and quantum dots. In these cases, a physical chemistry approach and standard recipes allow a good control of the size and shape of the resulting nano-objects. However, organometallic precursors have emerged as an important class allowing the preparation of a large variety of nano-objects, concerning a large number of elements and displaying a clean and controllable surface and therefore good physical and chemical properties. This perspective article is mostly devoted to the research efforts carried out by our group on the search for new classes of precursors and on the importance of knowing their exact structure and the molecular chemistry involved prior to the fabrication of the nano-objects.

The big impact of a small detail: cobalt nanocrystal polymorphism as a result of precursor addition rate during stock solution preparation.

The control of nanocrystal structures at will is still a challenge, despite the recent progress of colloidal synthetic procedures. It is common knowledge that even small modifications of the reaction parameters during synthesis can alter the characteristics of the resulting nano-objects. In this work we report an unexpected factor which determines the structure of cobalt nanoparticles. Nanocrystals of distinctly different sizes and shapes have resulted from stock solutions containing exactly the same concentrations of [Co{N(SiMe(3))(2)}(2)(thf)], hexadecylamine, and lauric acid. The reduction reaction itself has been performed under identical conditions. In an effort to explain these differences and to analyze the reaction components and any molecular intermediates, we have discovered that the rate at which the cobalt precursor is added to the ligand solution during the stock solution preparation at room temperature becomes determinant by triggering off a nonanticipated side reaction which consumes part of the lauric acid, the main stabilizing ligand, transforming it to a silyl ester. Thus, an innocent mixing, apparently not related to the main reaction which produces the nanoparticles, becomes the parameter which in fine defines nanocrystal characteristics. This side reaction affects in a similar way the morphology of iron nanoparticles prepared from an analogous iron precursor and the same long chain stabilizing ligands. Side reactions are potentially operational in a great number of systems yielding nanocrystals, despite the fact that they are very rarely mentioned in the literature.

Structural influence on the photochromic response of a series of ruthenium mononitrosyl complexes.

In mononitrosyl complexes of transition metals two long-lived metastable states corresponding to linkage isomers of the nitrosyl ligand can be induced by irradiation with appropriate wavelengths. Upon irradiation, the N-bound nitrosyl ligand (ground state, GS) turns into two different conformations: isonitrosyl O bound for the metastable state 1 (MS1) and a side-on nitrosyl conformation for the metastable state 2 (MS2). Structural and spectroscopic investigations on [RuCl(NO)py(4)](PF(6))(2)·1/2H(2)O (py = pyridine) reveal a nearly 100% conversion from GS to MS1. In order to identify the factors which lead to this outstanding photochromic response we study in this work the influence of counteranions, trans ligands to the NO and equatorial ligands on the conversion efficiency: [RuX(NO)py(4)]Y(2)·nH(2)O (X = Cl and Y = PF(6)(-) (1), BF(4)(-) (2), Br(-)(3), Cl(-) (4); X = Br and Y = PF(6)(-) (5), BF(4)(-) (6), Br(-)(7)) and [RuCl(NO)bpy(2)](PF(6))(2) (8), [RuCl(2)(NO)tpy](PF(6)) (9), and [Ru(H(2)O)(NO)bpy(2)](PF(6))(3) (10) (bpy = 2,2'-bipyridine; tpy = 2,2':6',2"-terpyridine). Structural and infrared spectroscopic investigations show that the shorter the distance between the counterion and the NO ligand the higher the population of the photoinduced metastable linkage isomers. DFT calculations have been performed to confirm the influence of the counterions. Additionally, we found that the lower the donating character of the ligand trans to NO the higher the photoconversion yield.

The three-dimensional intermolecular network formed via water molecules in trans-bis(nitrito-κN)tetrakis(pyridine-κN)ruthenium(II) dihydrate.

The molecular geometry of the tetragonal crystal structure of the title compound, [Ru(NO(2))(2)(C(5)H(5)N)(4)]·2H(2)O, differs from that previously determined by powder diffraction [Schaniel et al. (2010). Phys. Chem. Chem. Phys. 12, 6171-6178]. In the [Ru(NO(2))(C(5)H(5)N)(4)] molecule, the Ru atom lies at the intersection of three twofold axes (Wyckoff position 8b). It is coordinated by four N atoms of the pyridine rings, as well as by two N atoms of N-nitrite groups. The last two N atoms are located on a twofold axis (Wyckoff position 16f). The O atoms of the water molecules are situated on a twofold axis (Wyckoff position 16e). Short intermolecular contacts are observed in the crystal structure, viz. N-O···OW and N-O···H-OW contacts between nitrite and water, and weak C-H···OW hydrogen bonds between pyridine and water. Thus, the intercalated water molecules act as bridges connecting the trans-[Ru(NO(2))(2)(py)(4)] molecules into a three-dimensional network.

A facile route for the preparation of nanoparticles of the spin-crossover complex [Fe(Htrz)2(trz)](BF4) in xerogel transparent composite films.

Films and monoliths containing the spin crossover complex [Fe(Htrz)(2)(trz)](BF(4)) (trz = 1,2,4-triazole) as nanoparticles have been obtained. The dispersion and consecutive inclusion of the Fe complex in a silica matrix prepared from tetramethoxysilane or tetraethoxysilane afford monoliths or films with a violet colour at room temperature, which turns white above 380 K. This change of colour is reversible. This thermochromic behaviour has been characterized by measuring the magnetic properties together with thermogravimetric studies and Raman spectroscopy, the result of which all demonstrate that both films and monoliths undergo a spin crossover. Microscopy studies confirm the occurrence of the Fe complex as nanoparticles, in both the monoliths and the films. The facile synthesis of these materials as nanoparticles in transparent films should open the possibility of the synthesis of high quality films.

[Ru(py)4Cl(NO)](PF6)2.0.5H2O: a model system for structural determination and ab initio calculations of photo-induced linkage NO isomers.

Structure analysis of ground state (GS) and two light-induced (SI and SII) metastable linkage NO isomers of [Ru(py)4Cl(NO)](PF6)2.0.5H2O is presented. Illumination of the crystal by a laser with lambda = 473 nm at T = 80 K transfers around 92% of the NO ligands from Ru-N-O into the isomeric configuration Ru-O-N (SI). A subsequent irradiation with lambda = 980 nm generates about 48% of the side-on configuration Ru<(N)(O) (SII). Heating to temperatures above 200 K or irradiation with light in the red spectral range transfers both metastable isomers reversibly back to the GS. Photodifference maps clearly show the N-O configurations for both isomers and they could be used to find a proper starting model for subsequent refinements. Both metastable isomers have slightly but significantly different cell parameters with respect to GS. The main structural changes besides the Ru-O-N and RU<(N)(O) linkage are shortenings of the trans Ru-Cl bonds and the equatorial Ru-N bonds. The experimental results are compared with solid-state calculations based on density functional theory (DFT), which reproduce the observed structures with high accuracy concerning bond lengths and angles. The problem of how the different occupancies of SI and GS could affect refinement results was solved by a simulation procedure using the DFT data as starting values.

Photogeneration of two metastable NO linkage isomers with high populations of up to 76% in trans-[RuCl(py)4(NO)][PF6]2.1/2H2O.

Two light-induced metastable NO linkage isomers with oxygen-bound (SI) and side-on configuration (SII) of NO are generated in trans-[RuCl(py)(4)(NO)][PF(6)](2).(1/2)H(2)O. Irradiation by light in the blue-green spectral range (450-530 nm) leads to the population of SI. A further irradiation by near infrared light (920-1100 nm) transfers SI into SII at temperatures below 150 K. The heat release during the thermal decay of the linkage isomers shows that SI and SII are separated from the ground state (GS) by potential barriers of E(A)(SI) = 0.70(3) eV and E(A)(SII) = 0.38(3) eV, and are energetically situated at 1.42(6) eV and 1.07(7) eV above the ground state, respectively. Maximum populations of 76% for SI and of 56% for SII can be generated, as determined by the decrease of the nu(NO) stretching absorption band of the ground state. The nu(NO) stretching vibration shifts to lower energies by 143 cm(-1) in SI and by 300 cm(-1) in SII, indicating that the linkage isomers are of the same type as found in other octahedrally coordinated transition-metal nitrosyl complexes. The experimental observations are in agreement with results from calculations by the density functional theory, which predict that the metastable states correspond to a side-on bonded (SII) and an isonitrosyl (SI) configuration of the NO ligand. The calculations provide the energy minima of the ground state and the metastable states SI and SII as well as the saddle points along the reaction coordinate Q. This reaction coordinate corresponds to a rotation of the NO ligand by about 90 degrees (SII) and 180 degrees (SI), and therefore allows the comparison between observed and calculated activation energies.