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Title: Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

Abstract

Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal clustermore » complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
OSTI Identifier:
22443455
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 219; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AGGLOMERATION; DIMERS; ELECTRONS; HALIDES; HEXAGONAL LATTICES; LIGANDS; MONOCLINIC LATTICES; MONOCRYSTALS; RARE EARTHS; TETRAGONAL LATTICES; TRANSITION ELEMENTS; X-RAY DIFFRACTION

Citation Formats

Steinberg, Simon, Zimmermann, Sina, Brühmann, Matthias, Meyer, Eva, Rustige, Christian, Wolberg, Marike, Daub, Kathrin, Bell, Thomas, and Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms. United States: N. p., 2014. Web. doi:10.1016/J.JSSC.2014.07.012.
Steinberg, Simon, Zimmermann, Sina, Brühmann, Matthias, Meyer, Eva, Rustige, Christian, Wolberg, Marike, Daub, Kathrin, Bell, Thomas, & Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms. United States. doi:10.1016/J.JSSC.2014.07.012.
Steinberg, Simon, Zimmermann, Sina, Brühmann, Matthias, Meyer, Eva, Rustige, Christian, Wolberg, Marike, Daub, Kathrin, Bell, Thomas, and Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de. 2014. "Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms". United States. doi:10.1016/J.JSSC.2014.07.012.
@article{osti_22443455,
title = {Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms},
author = {Steinberg, Simon and Zimmermann, Sina and Brühmann, Matthias and Meyer, Eva and Rustige, Christian and Wolberg, Marike and Daub, Kathrin and Bell, Thomas and Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de},
abstractNote = {Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.},
doi = {10.1016/J.JSSC.2014.07.012},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 219,
place = {United States},
year = 2014,
month =
}
  • The technique of carbon-arc evaporation has been successfully utilized to encapsulate a wide variety of rare-earth species in carbon cages. The authors have observed M{sub m} @ C{sub n} (M = Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, or Er) species present in the toluene extracts of the carbon soot using laser desorption mass spectrometry. The presence of multiple-metal species appears to depend strongly on the metal-to-carbon atom ratio found in the starting rods, with the higher metal concentrations favoring multiple-metal incorporation. One often observed dimetallofullerene is M{sub 2}{degrees}C{sub 80}. Molecular orbital arguments are presented to support a possiblemore » icosahedral structure for C{sub 80}. 27 refs., 2 figs., 1 tab.« less
  • Syntheses of the title compounds result from appropriate reactions of the elements and RI{sub 3} (R=La, Pr) in sealed Nb containers at, variously, 800-990{degrees}C. The structures of three were detailed by single crystal X-ray diffraction: Pr{sub 4}I{sub 5}Ni, Pmmn, Z = 2, R(F)/R{sub w} = 3.6/5.3%; Pr{sub 3}I{sub 3}Os, P2{sub 1}/m, Z = 2, R/R{sub 2} 2.4/2.8%; Pr{sub 2}INi{sub 2}, P6{sub 3}/mmc, Z = 2, R/R{sub w} = 2.2/3.6. The new compounds La{sub 2}IZ{sub 2}, Z = Fe, Co, Ru, Os, were shown to be isostructural with Pr{sub 2}INi{sub 2}(Gd{sub 2}IFe{sub 2}) by Guinier powder diffraction. Pr{sub 4}I{sub 5}Ni, themore » first orthorhombic example among the R{sub 4}I{sub 5}Z series, consists of R{sub 6}Z octahedra condensed into chains. The new example contains the most extreme R:Z size proportions and clearly lacks the strong d{pi}-d{pi} bonding between Z and apical R seen within other members. Pr{sub 3}I{sub 3}Os, previously known only with a cubic Gd{sub 3}Cl{sub 3}C-(Ca{sub 3}I{sub 3}P-)-type structure, also occurs as a relatively undistorted member of the monoclinic Pr{sub 3}I{sub 3}Ru (double chain) family. Apical Pr-Os {pi}-bonding appears significant, with Pr-Os distances that are 0.24 {angstrom} shorter than the average within the waist of the parent octahedra. The R{sub 2}IZ{sub 2} phases expand the number of examples of the unusual Gd{sub 2}IFe{sub 2} structure, which contains AlB{sub 2}-like slabs; namely, graphite-like Z{sub 2} nets between eclipsed pairs of R layers that are in turn separated by single iodine layers. Notable distances in Pr{sub 2}INi{sub 2} are Ni-Ni, 2.36 {angstrom}, and Pr-Ni, 2.98 {angstrom}. Charge-consistent, extended Hueckel band calculations in La{sub 2}IFe{sub 2} (in contrast with results reported for Gd{sub 2}IFe{sub 2}) demonstrate a strong mixing of La-Fe and Fe-Fe bonding in a partially filled band, the Fe states on balance falling only slightly below those of La.« less
  • The new compound (IrCe{sub 3})I{sub 3} was synthesized by comproportionation reactions of stoichiometric ratios of CeI{sub 3}, Ce and Ir. Single crystal X-ray diffraction structure determination shows that (IrCe{sub 3})I{sub 3} crystallizes with the cubic variant of the (TR{sub 3})X{sub 3} family (I4{sub 1}32, Z=8, a=12.450(1) Å, V=1930.0(3) Å{sup 3}) and is isostructural with the recently reported (RuLa{sub 3})Br{sub 3}. Octahedral (IrCe{sub 6}) clusters share three common edges forming interpenetrating chains that run along the 4{sub 1} screw axes. Magnetic measurements on pure powder samples of (IrCe{sub 3})I{sub 3} show paramagnetic behavior and, at temperatures below 2 K, a mictomagneticmore » state. The isostructural (RuLa{sub 3})Br{sub 3} is a Pauli paramagnet suggesting metallic conductivity which is consistent with band structure calculations where the Fermi level is placed below a pseudogap. For (IrCe{sub 3})I{sub 3}, on the contrary, the Fermi level falls in a narrow gap rather than a pseudogap suggesting activated conductivity. - Graphical abstract: The subtle change from (RuLa{sub 3})Br{sub 3} to (IrCe{sub 3})I{sub 3} (IrCe{sub 3})I{sub 3} with the addition of one 5d and one 4f electron changes the magnetic and electronic properties dramatically; (RuLa{sub 3})Br{sub 3} is a Pauli paramagnet, (IrCe{sub 3})I{sub 3} a Langevin paramagnet with mictomagnetic behavior at very low temperatures. Display Omitted.« less
  • Rare-earth transition-metal (R-TM) alloys show superior permanent magnetic properties in the bulk, but the synthesis and application of R-TM nanoparticles remains a challenge due to the requirement of high-temperature annealing above about 800 degrees C for alloy formation and subsequent crystalline ordering. Here we report a single-step method to produce highly ordered R-TM nanoparticles such as YCo(5) and Y(2)Co(17), without high-temperature thermal annealing, by employing a cluster-deposition system and investigate their structural and magnetic properties. The direct ordering is highly desirable to create and assemble R-TM nanoparticle building blocks for future permanent-magnet and other significant applications.
  • Suitable reactions in sealed Nb tubing at 850-950 {degrees}C gave good yields of a family of oligomeric cluster phases that were characterized by single-crystal X-ray diffraction means. The basic Y{sub 16}Z{sub 4} units ({approximately}{bar 4} symmetry) can be derived from 2+2 condensation of centered Y{sub 6}Br{sub 12}Z-type clusters or as tetracapped truncated tetrahedra Y{sub 16} that are centered by a large tetrahedral Z{sub 4}. These are surrounded by 36 bromine atoms which bridge edges or cap faces of the Y{sub 16}Z{sub 4} nuclei and, in part, bridge to metal atoms in other clusters. The principal bonding appears to be Y-Zmore » and Y-Br, with weaker Y-Y ({bar d} {approximately} 3.70 {angstrom}) and negligible Z-Z interactions. The phase Y{sub 16}Br{sub 20}Ru{sub 4} (P4{sub 2}/nnm, Z = 2; a = 11.662(1) {angstrom}, c = 16.992 (2) {angstrom}) is isostructural with Y{sub 16}I{sub 20}Ru{sub 4} and with the new Sc{sub 16-} Br{sub 20}Z{sub 4} (Z = Fe, Os). Syntheses only in the presence of Ir and ABr-YBr{sub 3} fluxes (A = K-Cs) produce Y{sub 16-} Br{sub 24}Ir{sub 4} (Fddd, Z = 8; a = 11.718(3) {angstrom}, b = 22.361(7) {angstrom}, c = 44.702(2) {angstrom}), in which the electron-richer Ir interstitials are compensated by four additional bromine atoms and altered bridging between macroclusters. Larger amounts of YBr{sub 3} yield a third example, Y{sub 20}Br{sub 36}Ir{sub 4} (Y{sub 16}Br{sub 24}Ir{sub 4}{center_dot}4YBr{sub 3}, I4{sub 1}a, Z = 4; a = 12.699(1) {angstrom}, c = 45.11- (1){angstrom}). Here infinite zigzag chains of YBr{sub 6/2} octahedra that share cis edges lie between and bridge to the Y{sub 16}Ir{sub 4} clusters. All of these phases contain 60-electron, closed-shell macroclusters. Y{sub 16}Br{sub 20}Ru{sub 4} and Y{sub 20}Br{sub 36}ir{sub 4} were found to exhibit temperature-independent (Van Vleck) paramagnetism with values typical of those found for other rare-earth-metal, zirconium, niobium, and tantalum cluster halides.« less