Syntheses, Crystal and Electronic Structures, and Physical Properties of Quaternary Semiconductors: Ln₂Mn₃Sb₄S₁₂(Ln = Pr, Nd, Sm, Gd)

Abstract

Four new quaternary lanthanide antimony sulfides: Ln(2)Mn(3)Sb(4)S(12) (Ln = Pr, Nd, Sm, Gd) have been synthesized from a stoichiometric element mixture at 1373 K by conventional solid state reactions. These compounds crystallize in the monoclinic space group C2/m with the unit cell parameters of a = 19.928(2)-19.9672(6) A, b = 3.9323(4)-3.8803(2) A, c = 14.921(2)-14.9011(1) A, V = 938.5(2)-925.63(6) A(3), and Z = 2 on going from Ln = Pr to Gd. Their structure represents a novel wavy MnS(6) octahedron layer decorated on both sides by chains of an SbS(5) square pyramid via strong Sb-S bonding interactions (< 3.0 A). Such a MnS(6) octahedron layer consists of chains of an edge-sharing [Mn1S(6)](2) dimer extending along [010] that are interconnected by single strings of an edge-sharing Mn2S(6) octahedron at axial S apexes. Sm(2)Mn(3)Sb(4)S(12) displays spin-canted antiferromagnetic interactions between Sm(2+) and Mn(2+) centers and an optical gap of 1.50 eV. The DFT study indicates an indirect band gap with an electronic transfer excitation of S 3p to Sb 5p orbital electrons.

Synthesis, Crystal Structure, and NLO Property of the Chiral Sulfide Sm4InSbS9

“…Similarly, the fourth crystallographically independent Sm site, Sm4 has approximate mono‐capped trigonal prismatic environments with Sm–S contacts in the range of 2.76–3.11 Å. All these Sm–S distances are comparable to the normal range as in the related chalcogenides: Sm 4 GaSbS 9 (2.73–3.05 Å),9a Sm 2 Mn 3 Sb 4 S 12 (2.84–3.02 Å),8b Ba 4 Sm 2 Cd 3 S 10 (2.78–2.86 Å),25 CsSmGeS 4 (2.83–3.01 Å),26 and CsSmSiS 4 (2.83–3.04 Å) 27…”

“…Recently, many efforts on antimony sulfides have yielded several compounds with structural diversity and technologically important properties, such as, La 4 FeSb 2 S 10 ,8a RE 2 Mn 3 Sb 4 S 12 ( RE = Pr, Nd, Sm, Gd),8b RE 4 GaSbS 9 ( RE = Pr, Nd, Sm, Gd–Ho),9a and RE 4 InSbS 9 ( RE = La, Pr, Nd) 10. For RE 4 InSbS 9 ( RE = La, Pr, Nd), only La‐member exhibits second harmonic generation with an intensity of 1.50 times that of benchmark AgGaS 2 in type I phase‐matchable behavior.…”

Two Hybrid Polymeric Iodoargentates Incorporating Aromatic N-Heterocycle Derivatives as Electron Acceptors

“…These values are smaller than the experimental band gaps of 1 and 2, which might result from underestimation of the band gap by the density functional theory method. 15 The band structure of 1 displays similar gross characters along G−Y−A−B−D−E, due In summary, two new hybrid polymeric iodoargentates incorporating electron-acceptor phen/bpt molecules have been synthesized under hydrothermal conditions. 1 provides a new type of taenioid [Ag 2 I 2 ] n chain covalently bonding to bidentate-chelating phen molecules because the tetracoordinated Ag + ions of 1D iodoargentate [(AgI) x ] n (x = 1, 4, 6) backbones directly bond to monodentate ANDs.…”

Syntheses, structures, optical properties, and electronic structures of KBaMSe 3 (M = As, Sb)

“…Since the stereochemical activity of ns 2 lone pair of electrons of group 15 elements M (M = As, Sb, Bi) has profound effects on the crystal structures, electronic structures, and hence on the properties of the resultant compounds, the exploratory synthesis of new group 15 element-containing multinary chalcogenides has been an active area for years and with great efforts many chalcogenides with intriguing structures and properties have been discovered [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][24][25][26][27]. For example, Ba 23-Ga 8 Sb 2 S 38 features an unusual zero-dimensional structure containing totally isolated GaS 4 tetrahedra and discrete SbS 3 pyramids [2]; Bi 3 In 4 S 10 and Bi 14.7 In 11.3 S 38 contain interesting chains of Bi atoms with alternating short Bi-Bi bonds of around 3.1 Å and longer distances of around 4.6 Å [3]; Cs 5 BiP 4 Se 12 [4], Rb 3 Ta 2 AsS 11 [5], La 4 InSbS 9 [6], and Sm 4 GaSbS 9 exhibit very strong second harmonic generation (SHG) responses in the IR range [7].…”