Syntheses, Crystal Structures, and Properties of Six New Lanthanide(III) Transition Metal Tellurium(IV) Oxyhalides with Three Types of Structures

Abstract

Solid-state reactions of lanthanide(III) oxide (and lanthanide(III) oxyhalide), transition metal halide (and transition metal oxide), and TeO(2) at high temperature lead to six new lanthanide transition metal tellurium(IV) oxyhalides with three different types of structures, namely, DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, ErCuTe(2)O(6)Br, Sm(2)Mn(Te(5)O(13))Cl(2), Dy(2)Cu(Te(5)O(13))Br(2), and Nd(4)Cu(TeO(3))(5)Cl(3). Compounds DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, and ErCuTe(2)O(6)Br are isostructural. The lanthanide(III) ion is eight-coordinated by eight oxygen atoms, and the copper(II) ion is five-coordinated by four oxygens and a halide anion in a distorted square pyramidal geometry. The interconnection of Ln(III) and Cu(II) ions by bridging tellurite anions results in a three-dimensional (3D) network with tunnels along the a-axis; the halide anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels. Compounds Sm(2)Mn(Te(5)O(13))Cl(2) and Dy(2)Cu(Te(5)O(13))Br(2) are isostructural. The lanthanide(III) ions are eight-coordinated by eight oxygens, and the divalent transition metal ion is octahedrally coordinated by six oxygens. Two types of polymeric tellurium(IV) oxide anions are formed: Te(3)O(8)(4)(-) and Te(4)O(10)(4)(-). The interconnection of the lanthanide(III) and divalent transition metal ions by the above two types of polymeric tellurium(IV) oxide anions leads to a 3D network with long, narrow-shaped tunnels along the b-axis. The halide anions remain isolated and are located at the above tunnels. Nd(4)Cu(TeO(3))(5)Cl(3) features a different structure. All five of the Nd(III) ions are eight-coordinated (NdO(8) for Nd(1), Nd(2), Nd(4), and Nd(5) and NdO(7)Cl for Nd(3)), and the copper(I) ion is tetrahedrally coordinated by four chloride anions. The interconnection of Nd(III) ions by bridging tellurite anions resulted in a 3D network with large tunnels along the b-axis. The CuCl(4) tetrahedra are interconnected into a 1D two-unit repeating (zweier) chain via corner-sharing. These 1D copper(I) chloride chains are inserted into the tunnels of the neodymium(III) tellurite via Nd-Cl-Cu bridges. Luminescent studies show that ErCuTe(2)O(6)Cl and Nd(4)Cu(TeO(3))(5)Cl(3) exhibit strong luminescence in the near-IR region. Magnetic measurements indicate the antiferromagnetic interactions between magnetic centers in these compounds.

Rare‐Earth Cadmium Tellurite Chlorides with a Structural Type Exhibiting [Ln12(TeO3)12] Slabs Alternating with CdCl6 Octahedral Layers

“…These oxygen polyhedra are typical for Ln 3+ cations. The Ln–O distances (Table 1) lie within the ranges observed for other rare‐earth–tellurium oxyhalides [e.g., d (Sm–O) = 2.35–2.48 Å in Sm 2 MnTe 5 O 13 Cl 2 37].…”

YCu(TeO3)2(NO3)(H2O)3: a novel layered tellurite

“…1). These chains are the structural units, since they are linked further into layers only through (Shen & Mao, 2005). However, in the current compound, the {CuÁ Á ÁTe} squares are non-planar, so that the chain periodicity is doubled, and Cu does not have chloride as an additional ligand.…”

Das erste Alkalimetall‐Lanthanoid(III)‐Iodid‐Oxotellurat(IV): Na2Lu3I3[TeO3]4

“…Na 2 Lu 3 I 3 [TeO 3 ] 4 stellt nach HoCl[TeO 3 ] 1, Nd 5 O 4 Cl 3 [TeO 3 ] 2 8, den kupferhaltigen Beispielen CuDyCl[TeO 3 ] 2 und CuErBr[TeO 3 ] 2 9 sowie CuNd 4 Cl 3 [TeO 3 ] 5 9 prinzipiell erst das sechste Lanthanoid(III)‐Oxotellurat(IV)‐Derivat überhaupt dar, das nachweislich vollständig isolierte [TeO 3 ] 2– ‐Pyramiden enthält, nachdem sowohl in den ternären Verbindungen M 2 Te 3 O 9 ( M = Nd, Dy, Tm – Lu) [25–27], M 2 Te 4 O 11 ( M = Y, La – Nd, Sm – Lu) [28–34] und M 2 Te 5 O 13 ( M = Sc, Y, Dy–Lu) [34–39], als auch in allen anderen in der Einleitung aufgeführten Beispielen, Oligomere oder durch starke Sekundärkontakte verbundene Oxotellurat(IV)‐Aggregate vorliegen. Nachdem uns mittlerweile die Synthese einer ganzen Serie von zur Titelverbindung isotypen Na 2 M 3 X 3 [TeO 3 ] 4 ‐Vertretern ( X = Cl: M = Y, La, Sm, Dy, Tm; X = Br: M = La – Nd, Sm – Lu; X = I: M = Pr, Eu, Ho, Er, Yb, Lu) 40 mit Na 2 Lu 3 I 3 [TeO 3 ] 4 ‐Struktur gelungen ist, werden in Zukunft Untersuchungen zur Lumineszenz (z.…”

“…Darüber hinaus kennt man bereits auch einige gleichzeitig kationisch und anionisch derivatisierte Oxotellurate(IV), bei denen zusätzlich zu den Halogenid‐Anionen noch Übergangsmetall‐Kationen in die Strukturen eingebaut werden, wie z. B. Cu MX [TeO 3 ] 2 ( M = Dy und Er mit X = Cl; M = Er mit X = Br), CuDy 2 Br 2 Te 5 O 13 und MnSm 2 Cl 2 Te 5 O 13 oder CuNd 4 Cl 3 [TeO 3 ] 5 9.…”