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Daniel Rabinovich

Publications and source records attributed to Daniel Rabinovich.

13 recordsLinked to original sources

Generation and optical properties of monodisperse wurtzite-type ZnS microspheres.

Monodisperse wurtzite-type ZnS microspheres have been prepared by using glutathione (GSH) as a sulfur source at low reaction temperatures ranging from 160 to 210 degrees C. The diameter of the ZnS microspheres can be tuned from approximately 254 to approximately 597 nm by changing the reaction parameters such as temperature, molar ratio of reactants (GSH/Zn2+), and reaction medium (ethylenediamine or ammonia). Our results demonstrate that monodentate amines (ammonia) play the same role as that of bidentate amines (ethylenediamine) in the formation of the wurtzite-type ZnS microspheres. The formation process of the monodisperse ZnS microspheres consists of a GSH-dominated nucleation process and an amine-dominated assembly process. The as-synthesized monodisperse ZnS microspheres readily self-assemble into ordered hexagonal patterns and thus have potential applications as colloidal crystalline materials. Blue fluorescence emission peaks at 415 and 466 nm in wavelength, attributed to deep-trap emission, are observed at room temperature.

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Growth and optical properties of wurtzite-type CdS nanocrystals.

This paper reports wurtzite-type CdS nanostructures synthesized via a hydrothermal reaction route using dithiol glycol as the sulfur source. The reaction time was found to play an important role in the shape of the CdS nanocrystals: from dots to wires via an oriented attachment mechanism. This work has enabled us to generate nanostructures with controllable geometric shapes and structures and thus optical properties. The CdS nanostructures show a hexagonal wurtzite phase confirmed by X-ray diffraction and show no evidence for a mixed phase of cubic symmetry. The Raman peak position of the characteristic first-order longitudinal optical phonon mode does not change greatly, and the corresponding full width at half-maximum is found to decrease with the CdS shape, changing from nanoparticles to nanowires because of crystalline quality improvement. The photoluminescence measurements indicate tunable optical properties just through a change in the shape of the CdS nanocrystals; i.e., CdS nanoparticles show a band-edge emission at approximately 426 nm in wavelength, while the CdS nanowires show a band-edge emission at approximately 426 nm as well as a weaker trap-state green emission at approximately 530 nm in wavelength. These samples provide an opportunity for the study of the evolution of crystal growth and optical properties, with the shape of the nanocrystals varying from nearly spherical particles to wires.

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Tris(mercaptoimidazolyl)borate complexes of the coinage metals: syntheses and molecular structures of the first gold compounds and related copper and silver derivatives.

The first tris(mercaptoimidazolyl)borate complexes of gold, Au(Tm(tBu)) and (Tm(tBu))Au(PPh3), have been prepared and structurally characterized. Together with their copper and silver analogues M(Tm(tBu)) and (Tm(tBu))M(PPh3)(M = Cu, Ag), these compounds constitute the first two complete series of Tm(R) derivatives to be isolated for the coinage metals. In order to evaluate the steric and electronic effects of the bulky tert-butyl substituents in these species, comparative structural analyses with the known methyl-substituted analogue Ag(Tm(Me)) and various (Tm(Me))M(PR3) derivatives (M = Cu, Ag) are also presented.

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Mediator-template assembly of nanoparticles.

The ability to construct size- and shape-controllable architectures using nanoparticles as building blocks is essential for the exploration of nanoparticle-structured properties. This paper reports findings of an investigation of a mediator-template strategy for the size-controllable assembly of nanoparticles. This strategy explores multidentate thioether ligands as molecular mediators and tetraalkylammonium-capped gold nanoparticles (5 nm) as templates toward the preparation of size-controllable and monodispersed spherical assemblies ( approximately 20-300-nm diameters). The combination of the mediation force of the multidentate thioether and the hydrophobic force of the tetraalkylammonium template establishes the interparticle linkage and stability. The morphological properties of the spherical assemblies have been characterized using TEM, AFM, and SAXS techniques. The finding of the soft-hard nature of the nanoparticle assemblies and their interactions with contacting substrates could form the basis of a new strategy for manipulating nanoscale linkages between nanoparticle assemblies, soldering nanoelectronics, and constructing nanosensor devices. The intriguing light scattering and optical absorption properties in response to assembly, disassembly, sizing, and interparticle spacing parameters have been characterized by dynamic light scattering and spectrophotometric measurements. The discovery of the controlled disassembly into individual nanoparticles and the size regulation by a third capping component could form the basis for applications in controlled drug delivery. The fundamental basis for the mediator-template strategy as a versatile assembly technique is further discussed in terms of experimental and theoretical correlations of the morphological and optical properties.

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Manganese(I) poly(mercaptoimidazolyl)borate complexes: spectroscopic and structural characterization of Mn...H-B interactions in solution and in the solid state.

The manganese(I) tricarbonyl complexes (Bm(R))Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhBmMe)Mn(CO)3, the first bis(mercaptoimidazolyl)borate derivatives for this metal, have been readily prepared and fully characterized. In particular, the presence of three-center-two-electron Mn...H-B interactions in these species, both in solution and in the solid state, has been investigated using a combination of IR and NMR spectroscopies and, in the case of the methyl-, tert-butyl- and para-tolyl-substituted derivatives, by X-ray crystallography. To complement these synthetic and structural studies, the tris(mercaptoimidazolyl)borate complexes (TmMe)Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhTm(Me))Mn(CO)3, as well as the related pyrazolylbis(mercaptoimidazolyl)borate (pzBmMe)Mn(CO)3, have also been synthesized and characterized by a combination of analytical and spectroscopic techniques.

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Cobalt tris(mercaptoimidazolyl)borate complexes: synthetic studies and the structure of the first cobaltaboratrane.

The paramagnetic complexes (TmtBu)CoX (X = Cl, Br, I) have been readily prepared and structurally characterized and provide a convenient entry into cobalt(II) tris(mercaptoimidazolyl)borate chemistry. A number of derivatives, including mononuclear triphenylphosphine adducts [(TmtBu)Co(PPh3)]X and dinuclear compounds [Co2(TmtBu)2X]Y, have been prepared in order to ascertain whether cobalt is a reliable surrogate for zinc in biological systems, particularly in sulfur-rich coordination environments. The structure of the first cobaltaboratrane is also reported.

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Size-controlled assembly of gold nanoparticles induced by a tridentate thioether ligand.

The ability to control the size and shape of nanoparticle assemblies is essential for the ultimate applications in sensors, catalysis, medical diagnostics, information storage, and quantum computation. This report demonstrates a novel mediator-template strategy toward this ability by exploring molecular driving forces exerted by a tridentate thioether as a mediator and tetraoctylammonium bromide as a templating agent. A combination of the ligand mediation, the surfactant templating, and their relative concentrations served as the driving forces. This combination leads to unprecedented spherical assemblies of gold nanoparticles in controllable sizes via manipulation of the relative concentrations of mediating and templating components.

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Homoleptic group 12 metal bis(mercaptoimidazolyl)borate complexes M(Bm(R))2 (M = Zn, Cd, Hg).

The sodium salt of the bis(2-mercapto-1-methylimidazolyl)borate anion [Bm(Me)](-) and those of the new bis(2-mercapto-1-alkylimidazolyl)borates [Bm(R)](-) (R = Bz, Bu(t), p-Tol) have been readily obtained from NaBH(4) and the appropriate 2-mercapto-1-alkylimidazoles. To contrast the binding preferences of the group 12 metals in a sulfur-rich environment, the four complete series of homoleptic complexes M[Bm(R)](2) (M = Zn, Cd, Hg), including the first bis(mercaptoimidazolyl)borate derivatives of cadmium and mercury, have been prepared. X-ray diffraction studies of Cd[Bm(Me)](2) and M[Bm(tBu)](2) (M = Zn, Cd, Hg) show the presence of distorted tetrahedral [MS(4)] central cores supplemented by two weak vicinal M.H-B bonds, interactions which appear to be a common feature in the coordination chemistry of Bm(R) ligands. In the case of zinc, it has been found that only in the presence of bulky ligands, as in Zn[Bm(tBu)](2), may an unexpected expansion in the coordination number from four to six be induced. This observation suggests the viability of octahedral intermediates in the processes whereby certain zinc enzymes transfer or exchange metal ions.

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Novel spherical assembly of gold nanoparticles mediated by a tetradentate thioether.

The ability to construct three- and two-dimensional architectures via nanoscale engineering is important for emerging applications of nanotechnology in sensors, catalysis, controlled drug delivery, microelectronics, and medical diagnostics. In this paper, we report novel 3D assembly using multidentate molecular building blocks. It is demonstrated that the interparticle linking of gold nanoparticles (3.7 nm core size) by a tetradentate thioether, tetra[(methylthio)methyl]silane, leads to the formation of a spherical assembly. The spherical size (30-80 nm diameter) is dependent on reaction time and relative ratio of the building blocks. The novelty of this approach is the viability of multidentate thioethers to link nanoparticles and produce spherical assemblies that can be readily assembled and disassembled. The spherical assembly can also be partially "melted" depending on the nature of interfacial interactions between the assembly and the substrate. These unusual morphological properties in shape and surface interaction and the intriguing assembling-disassembling capabilities may form the basis of designing and fabricating novel functional nanostructures.

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One-Dimensional Copper(I) Coordination Polymers Based on a Tridentate Thioether Ligand.

The one-dimensional copper(I) coordination polymers Cu(3){MeSi(CH(2)SMe)(3)}(2)X(3) (X = Cl, Br) and [{MeSi(CH(2)SMe)(3)}Cu(NCMe)]Y (Y = OSO(2)CF(3), BF(4), PF(6)) were readily obtained in very good to excellent yields (80-95%) by reacting CuX or [Cu(NCMe)(4)]Y, respectively, with the tridentate thioether ligand MeSi(CH(2)SMe)(3) in acetonitrile. The new complexes were characterized by a combination of analytical and spectroscopic techniques, including electrospray ionization mass spectrometry and, for the bromo and hexafluorophosphate derivatives, single-crystal X-ray diffraction. Both complexes exhibit one-dimensional chain structures with approximately tetrahedral copper centers and bridging unidentate/bidentate thioether ligands.

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Tris[(alkylthio)methyl]silanes: Syntheses and Structures of Chromium, Molybdenum, and Tungsten Complexes with a Tripodal Thioether Ligand.

The first member of a new family of tripodal thioether ligands, the methyltris[(alkylthio)methyl]silanes MeSi(CH(2)SR)(3) (R = Me), has been synthesized and characterized. Reactivity studies lead to the isolation of the complete series of group 6 metal carbonyl derivatives {eta(3)-MeSi(CH(2)SMe)(3)}M(CO)(3) (M = Cr, Mo, W), whose structures have been determined by single-crystal X-ray diffraction. The three complexes are isomorphous and display distorted octahedral structures with face-capping tridentate thioether ligands. {eta(3)-MeSi(CH(2)SMe)(3)}Cr(CO)(3) is monoclinic, P2(1)/c, a = 8.1658(2) Å, b = 15.0563(2) Å, c = 26.5791(3) Å, beta = 90.3653(6) degrees, V = 3267.74(8) Å(3), Z = 8. {eta(3)-MeSi(CH(2)SMe)(3)}Mo(CO)(3) is monoclinic, P2(1)/c, a = 8.34630(6) Å, b = 15.2747(2) Å, c = 27.1865(4) Å, beta = 90.8987(9) degrees, V = 3465.44(10) Å(3), Z = 8. {eta(3)-MeSi(CH(2)SMe)(3)}W(CO)(3) is monoclinic, P2(1)/c, a = 8.1582(2) Å, b = 14.9903(2) Å, c = 26.7268(4) Å, beta = 90.6568(8) degrees, V = 3268.30(9) Å(3), Z = 8.

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