Nanostructuring in the process of the formation of mixed-anion compounds: Rare-earth borogermanates, germanophosphates, and borotungstates

Specific features of the textures (the preferred orientation of the nanometer building blocks) in the structures of mixed-anion compounds—rare-earth borogermanates, germanophosphates, and borotungstates that arise from the acid-base interaction in the Ln₂O₃-B₂O₃-GeO₂, Ln₂O₃-GeO₂-P₂O₅, and Ln₂O₃-B₂O₃-WO₃ systems (Ln = La-Gd)—have been studied. Based on characteristic texture traits, the mixed-anion compounds of early rare-earth elements can be divided into three groups: (i) Ln₂O₃: E_xO_y > 1, (ii) Ln₂O₃: E_xO_y = 1, and (iii) Ln₂O₃: E_xO_y < 1. Because of the dominant structural effect of the basic oxide Ln₂O₃ in the compounds of the first group, the structures of Nd₁₄O₈(BO₃)₆(GeO₄)₂ and Pr₁₁O₁₀(GeO₄)(PO₄)₃ are composed of infinite [LnO_n] bands and layers and discrete groups [EO_m] located in the interband and interlayer spaces. The dominant structural effect of the acid oxides [E_xO_y] in the compounds of the third group leads to the appearance of ring textures composed of [LnO_n], as well as to the appearance of chains and networks composed of [EO_m], in the structures of Ln(BGeO₅) and Ln(BO₂)(WO₄). Original Russian Text ￠ G.A. Bandurkin, N.N. Chudinova, G.V. Lysanova, K.K. Palkina, E.V. Murashcva, V.A. Krut’ko, G.M. Balagina, 2006, published in Zhurnal Neorganicheskoi Khimii, 2006, Vol. 51, No. 2, pp. 334–347.     

Isotropic cationic networks in the structures of rare earth compounds

The isotropic cationic networks (CNs) completing the anisotropic CNs ai isotropic CNs binary opposition are identical in the structures of various rare earth compounds.     

“Nonresonant” Capture Regime in Microwave Amplifiers

We study a new regime of electron–wave interaction in microwave amplifiers and demonstrate its efficiency for a wide class of devices. A mildly relativistic millimeter-wave free-electron maser is calculated as a particular system implementing this regime.     

Trends in the cation distribution in the structures of the compounds forming in the Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> systems

The cationic networks in the structures of the initial oxides and all binary and ternary compounds forming in the Ln₂O₃-GeO₂-P₂O₅ systems have been studied. In the phase diagrams of the Nd₂O₃-GeO₂-P₂O₅ and Er2O₃-GeO₂-P₂O₅ systems, the regions of the structural influence of individual compounds with topologically identical cationic networks—anisotropic (A), combined (C), and isotropic (I)—are united into common areas. The A: C: I area ratio is 1: 1: 1 in the neodymium system and 1.7: 1: 3.4 in the erbium system.     

Nanostructural oxide “memory” of rare earth molybdates

The structural aspects of the acid-base interaction in the course of formation of molybdates in the binary systems Ln₂O₃-MoO₃ have been considered. The structures of rare earth molybdates inherit infinite bands of {[LnO _n ]-[LnO _n ]} dimers from the structures of Ln₂O₃ oxides. The nanostructural oxide “memory” of molybdates implies that the dimers in these bands retain approximately nanometer sizes and predominant mutual orientation despite the fact that, as the Mo formula content increases, the types of polyhedra in the dimers change and the contacts between dimers and, eventually, between the polyhedra in these dimers are lost.     

Structure of the La12GdEuB6Ge2O34 borogermanate as probed by NMR and IR spectroscopy

The structure of fine crystalline borogermanate La₁₂GdEuB₆Ge₂O₃₄ has been studied by NMR and IR spectroscopy. It has been demonstrated that this compound is isostructural to the homonuclear Ln₁₄B₆Ge₂O₃₄ compounds (Ln = Pr-Gd) and crystallizes in space group P3₁. The rare-earth elements have been distributed over the LnO _n polyhedra in La₁₂GdEuB₆Ge₂O₃₄ by analogy with the known structures. Lanthanum can occupy positions with CN 7–10, and the symmetry of these LnO _n coordination polyhedra is not higher than C _2v . In the La₁₂GdEuB₆Ge₂O₃₄ structure, the LnO _n coordination polyhedra are formed by oxygen atoms of oxo groups and anions, some of the oxygen atoms being shared by LnO _n polyhedra. The BO₃ and GeO₄ groups in the structure are also bridging, i.e., are involved in bonding of LnO _n polyhedra. One of the B-O bonds in La₁₂EuGd(BO₃)₆(GeO₄)₂O₈ is elongated as compared with the B-O bond lengths in homonuclear compounds Pr₁₄(BO₃)₆(GeO₄)₂O₈ and Nd₁₄(BO₃)₆(GeO₄)₂O₈. In the La₁₂GdEuB₆Ge₂O₃₄ structure, germanium is located in isolated GeO₄ tetrahedra with distorted T _d symmetry. The local symmetry of lanthanum in fine crystalline La₁₂GdEuB₆Ge₂O₃₄ have been assessed using ¹³⁹La NMR (B ₀ = 7.04 T, room temperature). For comparison, binary lanthanum compounds with a simpler structure— LaBO₃, La(BO₂)₃, and La₂GeO₅—have been used. The spectra of all compounds are rather broad (ν_1/2 = 180–240 kHz). The ¹³⁹La NMR spectra of the LaBO₃, La(BO₂)₃, and La₁₂GdEu(BO₃)₆(GeO₄)₂O₈ borates show a signal at (1080 ± 40) ppm, which is absent in the spectrum of La₂GeO₅. The shape of the ¹³⁹La NMR spectra of La₁₂GdEu(BO₃)₆(GeO₄)₂O₈ and LaBO₃ is characterized by the second-order quadrupole splitting with a downfield shoulder. The similarity of these spectra points to close ¹³⁹La NMR chemical shifts of La₁₂GdEu(BO₃)₆(GeO₄)₂O₈ and LaBO₃. No quadrupole splitting was observed in the spectra of La(BO₂)₃ and La₂GeO₅.     

Nanostructuring in the process of formation of rare-earth tungstates

Studying the textures (the preferred orientation of the nanometer building blocks) in the structures of neodymium tungstates shows that infinite dimeric bands {[LnO_n]-[LnO_n]}-{[LnO_n]-[LnO_n]} in a fluoritelike structure field of the Nd₂O₃-WO₃ binary system undergo fragmentation and modification. The structural background (staggered arrangement of polyhedra) is determined by the like effects of both the basic oxide Ln₂O₃ (a fluorite-type structure) and the acid oxide WO₃ (a ReO₃-type structure).