Syntheses and Structures of the New Quaternary Rubidium Selenides RbLn2CuSe4 (Ln=Sm, Gd, Dy), Rb1.5Ln2Cu2.5Se5 (Ln=Gd, Dy), and RbSm2Ag3Se5

Huang, Fu Qiang; Ibers, James A.

doi:10.1006/jssc.2000.8661

Cited by 27 publications

(14 citation statements)

References 24 publications

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“…Those involving Ln reflect the lanthanide contraction. The ranges of bond lengths are consistent, for example, with those of 2.940(2)−3.019(2) Å for La−Se in β-BaLaCuSe 3 ; 3.018(2)−3.158(2) Å for Ce−Se in KCe 2 CuSe 6 ; 2.911(2)−3.079(2) Å for Pr−Se in Pr 3 InSe 6 ; 2.902(3)−2.949(3) Å for Nd−Se in Ba 4 Nd 2 Cd 3 Se 10 ; 2.8595(4)−3.0086(3) Å for Sm−Se in CsSm 2 CuSe 4 ; 2.8871(1)−2.928(1) Å for Gd−Se in BaGdAuSe 3 ; 2.8509(6)−2.9240(6) Å for Tb−Se in CsTb 2 Ag 3 Se 5 ; 2.822(1)−2.9385(8) Å for Dy−Se in RbDy 2 CuSe 4 ; 2.879(1)−2.910(1) Å for Y−Se in BaYAgSe 3 ; 3.4281(8)−3.9527(3) Å for Cs−Se in CsSm 2 CuSe 4 ; 2.544(4)−2.792(4) Å for Cd−Se in Ba 4 Nd 2 Cd 3 Se 10 ; and the Hg−Se distances of 2.608(2)−2.759(2) Å in RbHgSbSe 3 …”

Section: Resultssupporting

confidence: 71%

The CsLnMSe₃ Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

et al. 2003

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CsLnCdSe(3) (Ln = Ce, Pr, Sm, Gd, Tb, Dy, Y) and CsLnHgSe(3) (Ln = La, Ce, Pr, Nd, Sm, Gd, Y) have been synthesized at 1123 K. These isostructural materials crystallize in the layered KZrCuS(3) structure type in the orthorhombic space group Cmcm and are group X extensions of the previously characterized Zn compounds. The structure is composed of two-dimensional [LnMSe(3)] layers that stack perpendicular to [010] and are separated by layers of face- and edge-sharing CsSe(8) bicapped trigonal prisms. Because there are no Se-Se bonds in the structure of CsLnMSe(3) (M = Zn, Cd, Hg), the formal oxidation states of Cs/Ln/M/Se are 1+/3+/2+/2-. CsSmHgSe(3) does not adhere to the Curie-Weiss law, whereas CsCeHgSe(3) and CsGdHgSe(3) are Curie-Weiss paramagnets with micro (eff) values of 2.77 and 7.90 micro (B), corresponding well with the theoretical values of 2.54 and 7.94 micro (B) for Ce(3+) and Gd(3+), respectively. Single-crystal optical absorption measurements were performed with polarized light perpendicular to the (010) and (001) crystal faces of these materials. The band gaps of the (010) crystal faces range from 1.94 eV (CsCeHgSe(3)) to 2.58 eV (CsYCdSe(3)) whereas those of the (001) crystal faces span the range 2.37 eV (CsSmHgSe(3)) to 2.54 eV (CsYCdSe(3) and CsYHgSe(3)). The largest band gap variation between crystal faces is 0.06 eV for CsYCdSe(3). Theoretical calculations for CsYMSe(3) indicate that these materials are direct band gap semiconductors whose colors and optical band gaps are dependent upon the orbitals of Y, M, and Se.

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Section: Resultssupporting

confidence: 71%

The CsLnMSe₃ Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

et al. 2003

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“…The bond length Gd-Se (2.9341(7) A ˚) (Table 3) is in the range of corresponding bond lengths found in gadolinium selenides, such as the bond lengths 2.8956(10)-2.9665(5) A ˚for Gd-Se in RbGd 2 CuSe 4 . 18 The Gd-N bond lengths (2.578(4)-2.600(4) A ˚) are in the range observed in compound 1d. In 2c, a layer structure of [Ln(dien) 2 (m-SnSe 4 )]moieties perpendicular to the a axis is formed through weak N-H ◊ ◊ ◊ Se hydrogen bonds (Fig.…”

Section: Resultsmentioning

confidence: 81%

Effects of lanthanide metal size and amino ligand denticity on the solvothermal systems Ln/Sn/Se/en and Ln/Sn/Se/dien (Ln = lanthanide)

et al. 2011

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Two systems, Ln/Sn/Se/en and Ln/Sn/Se/dien, were investigated under solvothermal conditions, and novel lanthanide selenidostannates [{Ce(en)(4)}(2)(μ-Se(2))]Sn(2)Se(6) (1a), [{Ln(en)(3)}(2)(μ-OH)(2)]Sn(2)Se(6) (Ln = Pr(1b), Nd(1c), Gd(1d); en = ethylenediamine), [{Ln(dien)(2)}(4)(μ(4)-Sn(2)Se(9))(μ-Sn(2)Se(6))](∞) (Ln = Ce(2a), Nd(2b)), and [Hdien][Gd(dien)(2)(μ-SnSe(4))] (2c) (dien = diethylenetriamine) were prepared and characterized. Two structural types of lanthanide selenidostannates were obtained across the lanthanide series in both systems. In the Ln/Sn/Se/en system, two types of binuclear lanthanide complex cations [Ce(2)(en)(8)(μ-Se(2))](4+) and [{Ln(en)(3)}(2)(μ-OH)(2)](4+) (Ln = Pr, Nd, Gd) were formed depending on the Ln(3+) ions. The complex cations are compensated by the [Sn(2)Se(6)](4-) anions. In the Ln/Sn/Se/dien system, coordination polymer [{Ln(dien)(2)}(4)(μ(4)-Sn(2)Se(9))(μ-Sn(2)Se(6))](∞) and ionic complex [Hdien][Gd(dien)(2)(μ-SnSe(4))] are obtained along the lanthanide series, among which the μ(4)-Sn(2)Se(9), μ-Sn(2)Se(6) and μ-SnSe(4) ligands to the Ln(3+) ions were observed. The formation of title complexes shows the effects of lanthanide metal size and amino ligand denticity on the lanthanide selenidostannates. Complexes 1a-2c exhibit semiconducting properties with band gaps between 2.08 and 2.48 eV.

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“…These materials display a variety of layered and tunnel structure types in addition to interesting physical properties. Examples include RbLn 2 CuSe 4 (Ln = Sm, Gd, Dy), Rb 1.5 Ln 2 Cu 2.5 Se 5 (Ln = Gd, Dy), RbSm 2 Ag 3 Se 5 , BaLnMQ 3 (Ln = rare earth; M = Cu, Ag, Au; Q = S, Se, Te), − Ba 2 LnAg 5 S 6 (Ln = La, Y), KGd 2 CuS 4 , K 2 CeCu 2 S 4 , ALnCu 2 S 6 (A = K, Cs; Ln = La, Ce, Eu), − K 1.5 Dy 2 Cu 2.5 Te 5 , K 0.5 Ba 0.5 DyCu 1.5 Te 3 , ALnCuQ 3 (A = K, Cs; Ln = Ce, Th, U; Q = S, Se, Te), , K 2 CeAg 3 Te 4 , KCeCuTe 4 , and Rb 2 CeCu 3 Te 5 …”

Section: Introductionmentioning

confidence: 99%

Tuning of Optical Band Gaps: Syntheses, Structures, Magnetic Properties, and Optical Properties of CsLnZnSe₃ (Ln = Sm, Tb, Dy, Ho, Er, Tm, Yb, and Y)

et al. 2002

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Eight new quaternary selenides CsSmZnSe(3), CsTbZnSe(3), CsDyZnSe(3), CsHoZnSe(3,) CsErZnSe(3), CsTmZnSe(3), CsYbZnSe(3), and CsYZnSe(3) have been synthesized with the use of high-temperature solid-state experimental methods. These compounds are isostructural with KZrCuS(3), crystallizing with four formula units in the orthorhombic space group Cmcm. The structure of these CsLnZnSe(3) compounds is composed of [LnZnSe(3)(-)] layers separated by Cs atoms. The Ln atom is octahedrally coordinated by six Se atoms, the Zn atom is tetrahedrally coordinated by four Se atoms, and the Cs atom is coordinated by a bicapped trigonal prism of eight Se atoms. Because there are no Se-Se bonds in the structure, the oxidation state of Cs is 1+, that of Ln is 3+, and that of Zn is 2+. CsYbZnSe(3) exhibits an antiferromagnetic transition at 11 K, whereas CsSmZnSe(3) does not follow a Curie-Weiss law. The remaining rare-earth compounds are paramagnetic, and the calculated effective magnetic moments of the rare-earth ions agree well with their theoretical values. Optical absorption data on face-indexed single crystals of CsSmZnSe(3), CsErZnSe(3), CsYbZnSe(3), and CsYZnSe(3) demonstrate that the optical band gap changes by more than 0.75 eV with the composition and by as much as 0.20 eV with the crystal orientation. The optical band gaps range from 2.63 eV (CsSmZnSe(3), CsErZnSe(3)) to 1.93 eV (CsYbZnSe(3)) for the (010) crystal face and 2.56 eV (CsErZnSe(3)) to 1.88 eV (CsYbZnSe(3)) for the (001) crystal face. The difference in the optical band gap of the (010) face vs the (001) face varies from +0.05 eV (CsYbZnSe(3)) to +0.20 eV (CsSmZnSe(3)).

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Syntheses and Structures of the New Quaternary Rubidium Selenides RbLn2CuSe4 (Ln=Sm, Gd, Dy), Rb1.5Ln2Cu2.5Se5 (Ln=Gd, Dy), and RbSm2Ag3Se5

Cited by 27 publications

References 24 publications

The CsLnMSe₃ Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

The CsLnMSe₃ Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

Effects of lanthanide metal size and amino ligand denticity on the solvothermal systems Ln/Sn/Se/en and Ln/Sn/Se/dien (Ln = lanthanide)

Tuning of Optical Band Gaps: Syntheses, Structures, Magnetic Properties, and Optical Properties of CsLnZnSe₃ (Ln = Sm, Tb, Dy, Ho, Er, Tm, Yb, and Y)

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Syntheses and Structures of the New Quaternary Rubidium Selenides RbLn2CuSe4 (Ln=Sm, Gd, Dy), Rb1.5Ln2Cu2.5Se5 (Ln=Gd, Dy), and RbSm2Ag3Se5

Cited by 27 publications

References 24 publications

The CsLnMSe3 Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

The CsLnMSe3 Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

Effects of lanthanide metal size and amino ligand denticity on the solvothermal systems Ln/Sn/Se/en and Ln/Sn/Se/dien (Ln = lanthanide)

Tuning of Optical Band Gaps: Syntheses, Structures, Magnetic Properties, and Optical Properties of CsLnZnSe3 (Ln = Sm, Tb, Dy, Ho, Er, Tm, Yb, and Y)

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The CsLnMSe₃ Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

The CsLnMSe₃ Semiconductors (Ln = Rare-Earth Element, Y; M = Zn, Cd, Hg)

Tuning of Optical Band Gaps: Syntheses, Structures, Magnetic Properties, and Optical Properties of CsLnZnSe₃ (Ln = Sm, Tb, Dy, Ho, Er, Tm, Yb, and Y)