Thermostimulated formation of silver and gold nanoparticles in porous silicon dioxide matrices

Manifestations of thermostimulated formation and subsequent transformation of silver and gold nanoparticles in porous opal and Vycor glass matrices are studied using optical spectroscopy. Two temperature ranges for silver nanoparticles are revealed, where first-type particles transform into another type of particles. With gold nanoparticles in these matrices, a temperature range in which one type of particles transforms into another type is established. An effect of complete blackening of Vycor glass samples, caused by their annealing, is revealed, and a rationalization of this effect is given.     

H-bonding of complex indium thiocyanates with crown ether molecules

Supramolecular ensembles [In(H₂O)₄(NCS)₂][In(H₂O)₂(NCS)₄] · 2(18C6) (I) and [In(H₂O)₃(NCS)₃] · 18C6 (II) are synthesized and identified by the data of elemental analyses, IR spectra, and X-ray structure analysis for structure I and X-ray phase analysis for structure II. In spite of specific features of the H-bonding of the 18C6 molecules with the cationic, molecular, or anionic indium complexes, chain motives are observed in structures I and II.     

Ferrite-induced breakdown. Mechanism of induction by thermal surface explosion

The conditions are investigated for gas breakdown above an Ni–Zn (M4OONN) ferrite surface. The assumption that the discharge is initiated by a thermal explosion of a surface layer of the ferrite modified by current flowing through it is verified experimentally and theoretically. The electric and thermophysical properties of the (ferrite+annealed layer) system are determined. The experimentally observed temporal characteristics of the prebreakdown phase of the discharge and the dependences of the breakdown voltage on the discharge-circuit parameters are described within the framework of a single model.Translated from FIAN Preprint No. 120, Lebedev Physics Institute, Moscow, 1990.     

New Solvate Polymorphs of Lanthanide Trisacetylacetonates: Crystal Structures of [Ln(acac)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · Solv (Ln = Eu,Dy; Solv = Thf,H<Subscript>2</Subscript>O + EtOH,MeOH)

Solvate polymorphs of [Dy(acac)₃(H₂O)₂] · Thf, [Ln(acac)₃(H₂O)₂] · H₂O · EtOH (Ln = Eu, Dy) and [Dy(acac)₃(H₂O)₂] · 1.5MeOH, which belongs to a new structural type, are isolated as single crystals. The structures of the prepared compounds are determined by X-ray crystallography, and the effect of solvate molecules on their crystal structures is discussed.     

Aggregates of the [GaCl<Subscript>4</Subscript>]<Superscript>−</Superscript> anion and the [Ga(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>(NCS)<Subscript>3</Subscript>] complex with 18C6

The complex formation in the system GaCl₃-ROH-MNCS-18K6 is considered (ROH = MeOH, EtOH; M = Na, K; 18C6 is 1,4,7,10,13,16-hexaoxocyclooctadecane). Two modifications of [Na(18C6)][GaCl₄], namely, aggregates [Na(18C6)][GaCl₄](MeOH)_0.9(EtOH)_1.1 and [Ga(H₂O)₃(NCS)₃] · 18C6, are synthesized and identified. The ⁷¹Ga NMR (solutions) and X-ray diffraction studies showed that the compositions and structures of the title compounds are determined by the ratio of the competing acido ligands (Cl^? and NCS^?) in the reaction solution.     

Metal-metal bonding in tetracyanometalates (M=PtII, PdII, NiII) of monovalent thallium. Crystallographic and spectroscopic characterization of the new compounds Tl2Ni(CN)4 and Tl2Pd(CN)4

The new crystalline compounds Tl2Ni(CN)4 and Tl2Pd(CN)4 were synthesized by several procedures. The structures of the compounds were determined by single-crystal X-ray diffraction. The compounds are isostructural with the previously reported platinum analogue, Tl2Pt(CN)4. A new synthetic route to the latter compound is also suggested. In contrast to the usual infinite columnar stacking of [M(CN)4]2- ions with short intrachain M-M separations, characteristic of salts of tetracyanometalates of NiII, PdII, and PtII, the structure of the thallium compounds is noncolumnar with the two TlI ions occupying axial vertices of a distorted pseudo-octahedron of the transition metal, [MTl2C4]. The Tl-M distances in the compounds are 3.0560(6), 3.1733(7), and 3.140(1) A for NiII, PdII, and PtII, respectively. The short Tl-Ni distance in Tl2Ni(CN)4 is the first example of metal-metal bonding between these two metals. The strength of the metal-metal bonds in this series of compounds was assessed by means of vibrational spectroscopy. Rigorous calculations, performed on the molecules in D4h point group symmetry, provide force constants for the Tl-M stretching vibration constants of 146.2, 139.6, and 156.2 N/m for the NiII, PdII, and PtII compounds, respectively, showing the strongest metal-metal bonding in the case of the Tl-Pt compound. Amsterdam density-functional calculations for isolated Tl2M(CN)4 molecules give Tl-M geometry-optimized distances of 2.67, 2.80, and 2.84 A for M = NiII, PdII, and PtII, respectively. These distances are all substantially shorter than the experimental values, most likely because of intermolecular Tl-N interactions in the solid compounds. Time-dependent density-functional theory calculations reveal a low-energy, allowed transition in all three compounds that involves excitation from an a1g orbital of mixed Tl 6pz-M ndz2 character to an a2u orbital of dominant Tl 6pz character.