title: New metal chalcogenides found in MnN-1(Gd2-xInx)SN+2(N = 3, 4, 5): syntheses, structures, and magnetic properties.
abstract: Three new metal chalcogenides have been identified in MnN-1(Gd2-xInx)SN+2with N = 3, 4, and 5 via a flux-growth synthesis. All compounds crystallize in the same space group of orthorhombic Cmcm with cell constants: Mn2GdInS5(1), a = 3.789(1) Å, b = 12.411(1) Å, and c = 15.489(1) Å; Mn3Gd2S6(2), a = 3.778(1) Å, b = 12.505(2) Å, and c = 19.114(2) Å; Mn4Gd2S7(3), a = 3.769(1) Å, b = 12.466(2) Å, and c = 22.289(3) Å. Compounds 1-3 form a homologous series through the modulation of the MnS unit, whose structures represent a complete system of the corresponding lillianites (N1,N2L) of3,3L,4,4L and5,5L. The gradually wider slabs formed in the series result in a monotonic increase along the c dimensions from 1 to 3. Crystal 3 is the first to achieve a predicted structure of5,5L. Mn2GdInS5(1) displays a weak antiferromagnetic (AFM) ordering at 10 K and the Weiss constant (θ) of -0.76 K. Mn2Gd1.5In0.5S5(1a), an isostructure of 1, shifts the AFM transition temperature to 12 K and possesses a slightly larger θ constant of -6.06 K. Mn4Gd2S7(3), featuring the thickest slabs in this series, shows a significant antiferromagnetic behavior beginning at a high temperature of 70 K and has a largest θ constant of -40.25 K. A small amount of impurity α-Gd2S3with an AFM transition temperature around 4 K was characterized in sample 3, which does not interfere with the magnetic ordering of 3 at much higher temperatures. These magnetic chalcogenides display band gaps of 1.66 eV for 1, 1.75 eV for 1a, and 1.44 eV for 3.
authors.affiliation: Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan. hsukf@mail.ncku.edu.tw.
authors.forename: I C
authors.initials: IC
authors.lastname: Liang
authors.affiliation: Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan. hsukf@mail.ncku.edu.tw.
authors.forename: C Y
authors.initials: CY
authors.lastname: Weng
authors.affiliation: Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan. hsukf@mail.ncku.edu.tw.
authors.forename: C
authors.initials: C
authors.lastname: Huang
authors.affiliation: National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan.
authors.forename: C K
authors.initials: CK
authors.lastname: Chang
authors.affiliation: National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan.
authors.forename: H S
authors.initials: HS
authors.lastname: Sheu
authors.affiliation: Center for Condensed Matter Sciences, National Taiwan University, Taipei 106, Taiwan.
authors.forename: J G
authors.initials: JG
authors.lastname: Lin
authors.affiliation: Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan. hsukf@mail.ncku.edu.tw.
authors.forename: K F
authors.identifier: http://orcid.org/0000-0002-6495-8862
authors.initials: KF
authors.lastname: Hsu