From One-Dimensional Linear Chain to Two-Dimensional Layered

Article pubs.acs.org/crystal

From One-Dimensional Linear Chain to Two-Dimensional Layered Chalcogenides XBi4S7 (X = Mn, Fe): Syntheses, Crystal and Electronic Structures, and Physical Properties Zhong-Zhen Luo,†,‡ Chen-Sheng Lin,† Wen-Dan Cheng,*,† Wei-Long Zhang,† Yuan-Bing Li,†,‡ Yi Yang,†,‡ Hao Zhang,† and Zhang-Zhen He† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China ‡ University of Chinese Academy of Sciences, Beijing, 100039, P. R. China S Supporting Information *

ABSTRACT: Two ternary-layered chalcogenides, MnBi4S7 (1) and FeBi4S7 (2), have been synthesized by using a conventional solid-state reaction method with sealed evacuated quartz tubes. The two isostructural compounds crystallize in the monoclinic space group C2/m (12), with unit cell parameters (1/2) a = 12.916(12)/12.823(19) Å, b = 3.970(3)/3.987(6) Å, c = 11.0397(15)/11.878(18) Å, β = 104.755(14) /104.38(2), and Z = 2 at room temperature. The remarkable structural features of these are the one-dimensional Heisenberg antiferromagnetic (1D HAF) chain, 1∞[XS6], and the two-dimensional [Bi2S3] and [MBi2S4] layers built up from the 1D 1∞[XS6] chain, 1∞[BiS6], and 1∞[BiS5] double chains. Magnetic property measurements indicate strong predominance of antiferromagnetic (AFM) interactions, with Néel temperatures (TN) of 31 K for 1 and 67 K for 2, respectively. The density functional theory (DFT) study indicates that both compounds are indirect-band semiconductors with band gaps of 0.79 eV for 1 and 1.24 eV for 2, respectively.

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synthesized and characterized to enrich this family.9,10 During the last couple of years, compound FexPb4‑xSb4Se10 of 1D [Fe2Se10] double chains display ferromagnetism below 300 K and superparamagnetism at higher temperatures.11 And K2FeGe3Se8 of 1D [FeGeSe6] chains was synthesized, which exhibits an antiferromagnetic transition at ∼10 K.12 However, it is still a great challenge to explore and design new 1D HAF chain-shaped compounds (with the integer spin quantum number of S = 1, 2, ..., or half-integer spin quantum number of S = 1/2, 3/2, ...). In the X−Bi−S system, the Bi3+ cation not only exhibits several coordination environment types, such as trigonalpyramidal,13 square-pyramidal,14 octahedral,15 capped trigonalprismatic,16 and bicapped trigonal-prismatic coordination,17 but also has the so-called stereochemically active lone pair electrons, which could act as a “chemical scissors”.18 For the X−Bi−S (X = Mn, Fe) system, the only known compound is Mn0.695Bi2.2S3.95 in the ICSD database.19 Although compound FeBi4S7 was first synthesized by Sugaki et al. in 1972,20 its crystal structure and physical properties have never been determined. Thus, the research of the ternary X−Bi−S system

INTRODUCTION Low-dimensional transition metal chalcogenides have attracted much attention in material science, solid state chemistry, and crystal engineering. This is because these compounds are the potential targets to explore the interesting physical properties caused by the quantum many-body effects1 and potential applications, including thermoelectrical,2 nonlinear optical (NLO),3 electronic phenomena, and unusual magnetic properties.4 In particular, one-dimensional Heisenberg antiferromagnetic (1D HAF) chain compounds have still been a hot topic since Haldane’s theoretical prediction, which was made in 1983.5 Up to now, numerous studies have been carried out on 1D magnetic chalcogenides. In 1987, Bronger et al. reported the AFeQ2 (A = K and Rb, Q = S and Se) system of 1D [FeQ4/2] chains, which reveal magnetic structures in the antiferromagnetically ordered state.6 Moreover, compounds FeSb2Q4 (Q = S and Se) both present the crystal structure characteristics with 1D [FeQ6] single chains but show different magnetic properties. For instance, FeSb2S4 shares a spiral magnetic structure, while FeSb2Se4 shows a room temperature ferromagnetism structure.7 Excitedly, AgVP2S6 with a 1D HAF chain was reported as an S = 1 Haldane gap compound by Mutka et al. in 1995.8 In addition, the isostructural MPb4Sb6S14 (X = Mn, Fe) system with single magnetic 1D [MS6] straight chain, and FePb4Sb6S14 as a possible S = 2 Haldane system, was © 2013 American Chemical Society

Received: June 24, 2013 Revised: July 22, 2013 Published: July 24, 2013 4118

dx.doi.org/10.1021/cg4009398 | Cryst. Growth Des. 2013, 13, 4118−4124

Crystal Growth & Design

Article

was reinvestigated using conventional solid state reaction method in closed silica tubes in our laboratory. Consequently, two two-dimensional (2D)-layered compounds with 1D HAF chain, MnBi4S7 (1) and FeBi4S7 (2), which belong to the pavonite homologous series compounds, were obtained.21 In this study, we represent the syntheses, crystal and electronic structures, and optical and magnetic properties of the two compounds.

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Table 1. Crystal Data and Structural Refinement Details for Compounds 1 and 2

EXPERIMENTAL SECTION

Syntheses. The starting reagents were used as obtained in this work: Mn (99.6%, Alfa Aesar China Company, Ltd.), Fe (99.98%, Alfa Aesar China Company, Ltd.), Bi (99.999%, Sinopharm Chemical Reagent Company, Ltd.), and S (99.999%, Sinopharm Chemical Reagent Company, Ltd.). All reactants were mixed roughly and loaded into a graphite crucible sealing in the evacuated silica tube, which was placed and heated in a computer-controlled resistance furnace. MnBi4S7 (1). A mixture of Mn (14.8 mg, 0.27 mmol), Bi (224.8 mg, 1.08 mmol), and S (60.4 mg, 1.89 mmol) was heated to 923 K within 48 h (and then held for 72 h) under the operation by a temperature controller. Subsequently, the sample was slowly cooled to 673 K in 100 h, followed by cooling to room temperature in 20 h. Sheet black crystals in >50% yield (based on Mn) were obtained, which were stable in air and moisture conditions. FeBi4S7 (2). Compound 2 was obtained by the same procedure as for 1 but with Fe (15.0 mg, 0.27 mmol), Bi (224.7 mg, 1.08 mmol), and S (60.3 mg, 1.89 mmol) as starting complexes. Consequently, sheet crystals that were stable in air and moisture conditions in >60% yield (based on Fe) were obtained after cooling to 298 K in 20 h. Pure phases were produced by a stoichiometry mixture of the X/Bi/ S molar ratio of 1:4:7. The mixtures were both heated to 873 K in 24 h, kept at this temperature for 48 h, and then cooled down to 298 K in 15 h. The products were reground and heated again at the same temperature to improve the homogeneity and purity. X-ray Crystallography. Suitable single crystals of 1 and 2 were selected for indexing and intensity data collecting. The single-crystal Xray diffraction data of 1 and 2 were both collected on a Saturn724+ diffractometer equipped with a graphite-monochromated Mo Kα radiation source (λ = 0.71073 Å) at 293 K. The diffraction image collection and the area detector data process were performed by Rigaku CrystalClear (version 1.4.0). Lorentz and polarization factors corrections were applied to the intensity data. The multiscan method was used to the absorption corrections.22 The two crystal structures were solved by the direct methods and refined by full matrix leastsquares on F2 using SHELXL-97.23 All atoms, refined with anisotropic thermal parameters, were fully occupied in the structures. The final refined solutions were checked by using the ADDSYM algorithm in the program PLATON,24 and no missed or higher symmetry elements were found. In order to confirm the chemical composition of the title compounds, semiquantitative microprobe elemental analysis was performed on a field emission scanning electron microscope (FESEM, JSM6700F) equipped with an energy dispersive X-ray spectroscope (EDX, Oxford INCA). The EDX results confirm the Fe/ Bi/S molar ratio of 1.0:5.1:7.7 for 2, which was in reasonable agreement with the single-crystal X-ray structural refinement results (Figure S5 in the Supporting Information). Crystallographic data and structural refinements information for 1 and 2 are summarized in Table 1. The atomic coordinates, equivalent isotropic thermal parameters are summarized in Tables S1 of the Supporting Information, and important bond distances and angles for compounds are listed in Table S2 of the Supporting Information. ICSD Nos. 426004 and 426005 contain the supplementary crystallographic data for this paper. The data can be obtained from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany (fax: (49) 7247−808−666; e-mail: crysdata@fiz-karlsruhe.de) The powder X-ray diffraction patterns for 1 and 2 were recorded at room temperature on a Rigaku MiniFlex II diffractometer by using Cu Kα radiation (λ = 1.5406 Å). The scanning range is 5−85° in 2θ with a step width of 0.02°. The experimental powder XRD patterns are in

chemical formula

MnBi4S7 (1)

FeBi4S7 (2)

formula weight space group a (Å) b (Å) c (Å) β (°) V (Å3), Z ρcal (g cm−3) absorption correction μ (mm−1) crystal size (mm) F(000) R1a, wR2b, for I > 2σ(I) R1a, wR2b, for all data GOF on F2

1115.35 C2/m 12.916(12) 3.970(3) 11.831(10) 104.755(14) 586.7(9), 2 6.314 multiscan 62.023 0.18 × 0.17 × 0.13 938 0.0370, 0.0674 0.0686, 0.0826 0.805

1116.26 C2/m 12.823(19) 3.987(6) 11.878(18) 104.38(2) 588.2(15), 2 6.303 multiscan 62.024 0.20 × 0.17 × 0.15 940 0.0420, 0.0937 0.0528, 0.0997 0.987

R1 = ∑∥Fo| − |Fc∥/∑|Fo| ∑w(Fo2)2]1/2

a

b

wR2(Fo2) = [∑w(Fo2 − Fc2)2/

good agreement with the simulated patterns generated using the CIF of each refined structure (Figure S1 of the Supporting Information). UV−vis Spectroscopy Measurements. The UV−vis diffuse reflectance spectra of the title compounds were recorded in the range of 400−2500 nm with a PerkinElmer Lambda 900 UV−vis spectrometer at 298 K. The BaSO4 standard white board was used as the comparison standard (100% reflectance). Absorption (α/S) data were converted from diffuse reflectance spectra using the Kubelka− Munk function, α/S = (1 − R)2/2R, where R is the reflectance coefficient and α and S are the absorption and scattering coefficient.25 Electronic Structure Calculations. The band structures and density of states (DOS) calculations of 1 and 2 were carried out using the Vienna Ab-initio Simulation Package (VASP)26 for further understanding and interpretation of the electronic, optical, and magnetic properties. The approach was based on an iterative solution of the Kohn−Sham equations within the DFT in a plane-wave basis set with a frozen-core projector-augmented wave (PAW) method.27 Electronic exchange correlation was dealt with the Perdew−Burke− Ernzerhof (PBE) function of the generalized-gradient approximation (GGA).28 The plane-wave cutoff energy and the energy converge criteria were set to be 350 eV and 1 × 10−6 eV/atom. And valence electronic configuration for the component element is S 3s23p4, Mn 3d54s2, Fe 3d64s2, and Bi 6s26p3. There are no further optimizations for the experimental crystal structure data that take into account the effect of the spin-polarization in this calculation. The onsite coulomb U and exchange J interactions of the localize d electron was represented by Dudarev’s LDA + U scheme,29 where the effective U−J value was set as 0.0 eV for Mn and 4.0 eV for Fe. The Monkhorst−Pack scheme30 k-point grid density of 2 × 3 × 2 was used for compounds 1 and 2. Magnetic Susceptibility. The direct-current magnetic measurements were performed using a Quantum Design MPMS-XL SQUID magnetometer at a magnetic field of 5000 Oe in the temperature range of 2−300 K. The susceptibility data from the Néel temperature (TN) up to 300 K was used to fit the Curie−Weiss equation χ = C/(T − θ) with a Curie constant (C) and a Curie−Weiss temperature (θ). The effective magnetic moments (μeff) of title compounds were calculated from the equation μeff = (7.997C)1/2 μB.31

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RESULTS AND DISCUSSION Structure Description. The title compounds crystallize in the monoclinic C2/m space group and feature 2D-layered structures, based on the 1D 1∞[XS6] chain, 1∞[BiS6], and ∞ 1 [BiS5] double chains. For simplicity, we take 1 as a representative to illustrate their structure characters. The 2D 4119



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crystal structure of 1 was formed by the neutral [Bi2S3] and [MnBi2S4] layers, which parallel to the (001) plane along the c axis direction. The two kinds of layers are connected by the S atoms, which are apex-shared by MnS6 and BiS6 octahedrons (Figure 1).

Figure 1. Approximate (010) structure view of 1. Bright black, green, and yellow balls represent Bi, Mn, and S atoms, respectively.

Figure 3. The structures of (a) 1∞[Bi(1)S6] and (b) 1∞[Bi(2)S5] double chains in 1. Bright black and yellow balls represent Bi and S atoms, respectively.

There are two crystallographically different bismuth atoms, one manganese (or iron) atom, and four different sulfur atoms, which are all fully sited on the Wyckoff positions without disordered atoms occupancy. The Bi(1) atom is coordinated by six S atoms and exhibits distorted octahedral coordination, with the Bi(1)−S distances ranging from 2.710 to 2.909 Å. However, the Bi(2) atom is coordinated by five S atoms and presents distorted square-pyramidal coordination, with the Bi(2)−S distances ranging from 2.608 to 3.033 Å (Figure 2). These Bi−

along the b axis and edges with the other two neighboring square-pyramids, are formed and indicated in Figure 3b. The MnS6 octahedrons are connected to each other by edge sharing and form an infinite 1D HAF 1∞[MnS6] chain. The paralleled ∞ ∞ 1 [Bi(2)S5] double chains and 1 [MnS6] chains are connected to each other by sharing the edges of the Bi(2)S5 squarepyramids and MnS6 octahedrons along the a axis direction and form the 2D [MnBi2S4] layer. For the chemically related phase, Mn0.695Bi2.2S3.95,19 also crystallizes in the monoclinic C2/m space group and features a 2D-layered structure (Figure 4). By

Figure 2. Local coordination environments of Bi atoms in 1. Long Bi2−S2 interactions are indicated by dashed lines.

S distances are comparable to that of 2.625−3.125 Å in Tl3Bi3(PS4)4.32 All X atoms are coordinated to six S atoms, forming XS6 octahedrons, which are slightly distorted from the regular octahedral coordination: two shorter X−S bonds of S(1) (2.493 Å for Mn and 2.419 Å for Fe) and four longer ones of S(3) (2.722 Å for Mn and 2.700 Å for Fe). These bond lengths are close to those of 2.430 to 2.775 Å of Mn−S in Sm2Mn3Sb4S1233 and 2.256 to 2.792 Å of Fe−S in FeMo2S4.34 The Bi(1)S6 octahedrons stack on top of each other by sharing the edge along the b axis and edges with the other two neighboring Bi(1)S6 octahedrons and string to make infinite ∞ 1 [Bi(1)S6] double chains (Figure 3a). These paralleled ∞ 1 [Bi(1)S6] double chains are connected to each other by sharing the edge of the Bi(1)S6 octahedrons along the a axis direction and forming the 2D [Bi2S3] layer. Similarly, the ∞ 1 [Bi(2)S5] square-pyramid double chains, sharing the edge

Figure 4. Approximate (010) structure view of Mn0.695Bi2.2S3.95. Bright black, green, turquoise, and yellow balls represent Bi, Mn, MnBi, and S atoms, respectively.

comparison, in Mn0.695Bi2.2S3.95, there are three and two crystallographically independent bismuth and manganese atoms, respectively. Moreover, the [(MnBi)BiS] layer for Mn0.695Bi2.2S3.95 and [Bi2S3] layer for 1 have different structure types. In Mn0.695Bi2.2S3.95, the paralleled 1∞[Bi(1)S6] double chains and 1∞[Mn(1)Bi(3)S6] chains are connected to each other by sharing the edge of the Bi(1)S6 octahedrons and Mn(1)Bi(3)S6 octahedrons along the a axis direction and form the 2D [(MnBi)BiS] layer. However, the [Bi2S3] layer is formed just by the 1∞[Bi(1)S6] double chains in 1. 4120



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Figure 5 illustrates the 1D HAF straight chain of 1∞[MnS6], which was formed by edge sharing of the MnS6 octahedrons.

Figure 6. Optical diffuse reflectance spectra for 1 (red) and 2 (blue).

compounds. The TDOS and PDOS of 1 are discussed as a representative under the similar DOS of the two compounds. As seen from Figure 7, the occupied states with energy ranging from −6.0 eV to the highest occupied states (the Fermi level), mainly contain S 3p and Mn 3d states with a little mixture of Bi 6s and Bi 6p states. And the lowest unoccupied states from 0.8 to 4.0 eV mostly involve unoccupied Bi 6p and Mn 3d states and some mixture of the S 3p state. In accordance with the results above and the charge distribution of HVB and LCB in Figure S2 of the Supporting Information, it is obvious that the charges transferring from the occupied S 3p and Mn 3d states to the unoccupied Bi 6p state make the main contributions to the optical diffuse reflectance spectra of 1. By comparing the HVB charge distributions between the two compounds, it is clear that the Mn 3d state contributes more than that of the Fe 3d state. Since the chemical potential of Mn2+ (15.64 eV) is slightly lower than that of Fe2+ (16.18 eV) and the more component of Mn in the HVB, the band gap of 1 is smaller than that of 2 (Figure 6). Magnetic Properties. The molar magnetic susceptibilities of compounds XBi4S7 (X = Mn, Fe) were measured at a magnetic field of 5000 Oe in the temperature range of 2−300 K. As can be seen in Figure 8, the magnetic susceptibility shows a maximum peak at 31 and 67 K for compounds 1 and 2, respectively, which indicates the predominance of antiferromagnetic interactions below their Néel temperature (TN). Above the TN, the magnetic susceptibility data obey the Curie− Weiss equation, χ = C/(T − θ). The linear fitting of the 1/χ versus T plots yield the values of C and θ for the two compounds, as shown in Table 2. The negative θ values, −57.53 K for 1 and −302.91 K for 2, suggest that a considerably antiferromagnetic couple dominate the exchange between the Mn2+ or Fe2+ centers. As can be seen in Figure S3 of the Supporting Information, there are two possible types of AFM configurations. One is that the neighboring XS6 octahedrons have the same spin, and the neighboring 1∞[XS6] chains have different spins in the [XBi2S4] layer (line up−up). The other is that each neighboring XS6 octahedrons have different spins in the intrachain (line up− down). The total energy calculation results in Table 3 indicate that the first configuration (line up−up) has higher energy than that of the second (line up−down). Consequently, these calculations indicate that the materials likely host 1D intrachain AF correlations.

Figure 5. Some important bond distances and angles in the 1∞[MnS6] chain substructure of 1.

The shortest intrachain Mn−Mn ions distance is d1 = 3.970 Å (d1 = 3.987 Å for Fe). The first nearest and second nearest neighbor Mn−Mn distances in the interchain are d2 = 6.756 Å and d3 = 12.479 Å (d2 = 6.714 Å and d3 = 13.421 Å for Fe), respectively. The ratio of d2/d1 is about 1.7, which implies small interchain spin correlations. Each 1∞[XS6] chain is separated by the 1∞[Bi(2)S5] double chains and [Bi2S3] layer, thus 1∞[XS6] can be seen as an isolated single magnetic straight chain (Figure 1). As stated above, the pronounced 1D magnetic character may be expected for the two compounds. Optical Properties. The optical band gaps of the title compounds were converted from the Kubelka−Munk equation in Figure 6, which gave the experimental band gap of 0.84 and 1.30 eV for 1 and 2, respectively. These results indicate that both of them are semiconductors and consistent with their black color. In the next section, the results of the electronic band structure calculation have explained why the band gap of 1 is smaller than that of 2. Electronic Band Structure and Density of States (DOS). The calculated band structures and density of states (DOS) of 1 and 2 along high symmetry points in the first Brillouin zone (BZ) were plotted in Figure S2 of the Supporting Information. It is shown that the highest occupied valence band (HVB) and the lowest unoccupied conduction band (LCB) of the two compounds are both located at the C and Γ points with the band gaps of 0.79 eV for 1 and 1.24 eV for 2, respectively. Consequently, both the compounds are considered to be the indirect band gap semiconductors and the calculated values of the band gaps are consistent with the experimental results. Figure 7 schematically displays the total density of states (TDOS) and partial density of states (PDOS) for the title 4121



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Figure 7. TDOS and PDOS of (a) 1 and (b) 2.

Supporting Information, approximate linear increasing magnetizations observed agree with the antiferromagnetic ordering below 31 K for 1 and 68 K for 2, respectively.35

For the sake of comparison, the experimental effective magnetic moment and spin-only magnetic moment of the titled compounds are listed in Table 2. For compound 1, the experimental μeff was calculated to be 5.67(4) μB from the magnetic susceptibility data. The result is a little smaller than the calculated value [5.91(6) μB] of the Mn2+ (d5, S = 5/2) ion based on the spin-only magnetic moment. Thus, it is evident that Mn2+ ions have high-spin states (t2g3eg2) in the octahedron MnS6 configuration. Similarly, for the Fe2+ ions in 2, the experimental μeff is 4.60(1) μB, which is smaller than that of 4.90(6) μB obtained by the Fe2+ (d6, S = 2) ion spin-only magnetic moment. It illustrates that the Fe2+ ions have highspin states (t2g4eg2) in the octahedron FeS6 configuration. Magnetization curve for 1 and 2 is considered to be a function of the applied field (H) at T = 2 K in Figure S4 (see the Supporting Information). As can be seen in Figure S4 of the

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CONCLUSIONS In summary, two ternary transition metal bismuth chalcogenides, MnBi4S7 and FeBi4S7, with 2D layered structure characteristics have been synthesized and characterized. The 2D layers are built up from the 1D HAF 1∞[XS6] chain (S = 5/ 2 for Mn, S = 2 for Fe) together with 1∞[BiS6] and 1∞[BiS5] double chains. Magnetic measurements at low temperature indicate that the two compounds are both AFM materials with TN of 31 K for 1 and 67 K for 2, respectively. In accordance with the effective magnetic moment of 5.67(4) μB for Mn2+ (1) and 4.60(1) μB for Fe2+ (2), the high-spin state can be assigned to Mn2+ (d5) and Fe2+ (d6) ions in the octahedral XS6 4122



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Figure 8. Plots of 1/χ vs T (black line) and χ vs T (blue line) for compounds: (a) 1 and (b) 2 in the temperature range of 2−300 K. The red line represents the best fit to the Curie−Weiss law.

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Table 2. Magnetic Properties of MnBi4S7 and FeBi4S7 −1

μeff (μB)

μ (μB)

C (emu K mol )

θ (K)

experiment

theory

4.03 2.65

−57.53 −302.91

5.67(4) 4.60(1)

5.91(6) 4.90(6)

MnBi4S7 FeBi4S7

S Supporting Information *

The experimental and simulated X-ray diffraction patterns, Xray crystallographic files in CIF format, electronic energy band structures, M (magnetization) versus H (magnetic field) curves of 1 and 2, and EDX spectrum. This material is available free of charge via the Internet at http://pubs.acs.org.

Table 3. The Energy Calculation Results for Compounds MnBi4S7 and FeBi4S7

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energy (eV) chemical formula

line up−down

line up−up

MnBi4S7 FeBi4S7

−231.86940 −219.33368

−231.84881 −219.32854

ASSOCIATED CONTENT

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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configuration. The experimental optical band gaps are 0.84 eV for 1 and 1.30 eV for 2, which are comparable to the values of 0.79 eV for 1 and 1.24 eV for 2 from the first-principles electronic structure calculations performed with the DFT. Comparisons between the HVB charge distribution of the two compounds indicate that the additional contribution of the Mn 3d state makes the band gap of 1 smaller than that of 2.

ACKNOWLEDGMENTS

This investigation was based on work supported by the National Natural Science Foundation of China under Grants 21173225, 91222204, and 21101156, and the Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry. 4123



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(27) Blöchl, P. E. Phys. Rev. B 1994, 50, 17953. (28) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. (29) Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188. (30) Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. C.; Humphreys, J.; Sutton, A. P. Phys. Rev. B 1998, 57, 1505. (31) O’Connor, C. J. Prog. Inorg. Chem. 1982, 29, 203−283. (32) Gave, M. A.; Malliakas, C. D.; Weliky, D. P.; Kanatzidis, M. G. Inorg. Chem. 2007, 46, 3632−3634. (33) Zhao, H. J.; Li, L. H.; Wu, L. M.; Chen, L. Inorg. Chem. 2010, 49, 5811−5817. (34) Vaqueiro, P.; Kosidowski, M. L.; Powell, A. V. Chem. Mater. 2002, 14, 1201−1209. (35) Zhang, W. L.; Cheng, W. D.; Zhang, H.; Geng, L.; Li, Y. Y.; Lin, C. S.; He, Z. Z. Inorg. Chem. 2010, 49, 2550−2556.

REFERENCES

(1) Miller, J. S. Extended Linear Chain Compounds; Plenum: New York, 1982; Vols. 1−3. (2) (a) Hsu, K.-F.; Chung, D.-Y.; Lal, S.; Mrotzek, A.; Kyratsi, T.; Hogan, T.; Kanatzidis, M. G. J. Am. Chem. Soc. 2002, 124 (11), 2410− 2411. (b) Chung, D.-Y.; Hogan, T. P.; Rocci-Lane, M.; Brazis, P.; Ireland, J. R.; Kannewurf, C. R.; Bastea, M.; Uher, C.; Kanatzidis, M. G. J. Am. Chem. Soc. 2004, 126, 6414−6428. (c) Rieger, F.; Mudring, A. V. Chem. Mater. 2007, 19 (2), 221−228. (d) Chung, I.; Biswas, K.; Song, J. H.; Androulakis, J.; Chondroudis, K.; Paraskevopoulos, K. M.; Freeman, A. J.; Kanatzidis, M. G. Angew. Chem., Int. Ed. 2011, 50 (38), 8834−8838. (3) (a) Nguyen, S. L.; Jang, J. I.; Ketterson, J. B.; Kanatzidis, M. G. Inorg. Chem. 2010, 49 (20), 9098−100. (b) Bera, T. K.; Jang, J. I.; Ketterson, J. B.; Kanatzidis, M. G. J. Am. Chem. Soc. 2008, 131 (1), 75−77. (4) (a) Baranov, A. I.; Isaeva, A. A.; Kloo, L.; Popovkin, B. A. Inorg. Chem. 2003, 42 (21), 6667−6672. (b) Huang, F. Q.; Somers, R. C.; McFarland, A. D.; Van Duyne, R. P.; Ibers, J. A. J. Solid State Chem. 2003, 174 (2), 334−341. (c) Yao, J.; Wells, D. M.; Chan, G. H.; Zeng, H.-Y.; Ellis, D. E.; Van Duyne, R. P.; Ibers, J. A. Inorg. Chem. 2008, 47 (15), 6873−6879. (d) Oh, G. N.; Choi, E. S.; Ibers, J. A. Inorg. Chem. 2012, 51 (7), 4224−30. (5) Haldane, F. D. M. Phys. Rev. Lett. 1983, 50, 1153. (6) Bronger, W.; Kyas, A.; Muller, P. J. Solid State Chem. 1987, 70, 262−270. (7) (a) Buerger, M. J.; Hahn, T. Am. Mineral. 1955, 40, 226. (b) Winterberger, M.; André, G. Phys. B (Amsterdam, Neth.) 1990, 162, 5. (c) Djieutedjeu, H.; Poudeu, P. F.P.; Takas, N. J.; Makongo, J. P. A.; Rotaru, A.; Ranmohotti, K. G. S.; Anglin, C. J.; Spinu, L.; Wiley, J. B. Angew. Chem., Int. Ed. 2010, 49 (51), 9977−9981. (8) Mutka, H.; Payen, C.; Molinie, P.; Escleston, R. S. Phys. B (Amsterdam, Neth.) 1995, 213-214, 170−172. (9) Matsushita, Y.; Ueda, Y. Inorg. Chem. 2003, 42, 7830−7838. (10) Leone, P.; Le Leuch, L. M.; Palvadeau, P.; Molinie, P.; Moelo, Y. Solid State Sci. 2003, 5, 771−776. (11) Poudeu, P. F. P.; Takas, N.; Anglin, C.; Eastwood, J.; Rivera, A. J. Am. Chem. Soc. 2010, 132, 5751−5760. (12) Feng, K.; Wang, W. D.; He, R.; Kang, L.; Yin, W. L.; Lin, Z. S.; Yao, J. Y.; Shi, Y. G.; Wu, Y. C. Inorg. Chem. 2013, 52, 2022−2028. (13) Geng, L.; Cheng, W. D.; Zhang, W. L.; Li, Y. Y.; Luo, Z. Z.; Zhang, H.; Lin, C. S.; He, Z. Z. Dalton Trans. 2011, 40 (17), 4474− 4479. (14) Geng, L.; Cheng, W. D.; Lin, C. S.; Zhang, W. L.; Zhang, H.; He, Z. Z. Inorg. Chem. 2011, 50 (12), 5679−5686. (15) Chung, D.-Y.; Iordanidis, L.; Rangan, K. K.; Brazis, P. W.; Kannewurf, C. R.; Kanatzidis, M. G. Chem. Mater. 1999, 11 (5), 1352− 1362. (16) Iordanidis, L.; Schindler, J. L.; Kannewurf, C. R.; Kanatzidis, M. G. J. Solid State Chem. 1999, 143, 151−162. (17) Wang, L.; Hung, Y. C.; Hwu, S. J.; Koo, H. J.; Whangbo, M. H. Chem. Mater. 2006, 18 (5), 1219−1225. (18) Zhang, W. L.; Cheng, W. D.; Zhang, H.; Geng, L.; Lin, C. S.; He, Z. Z. J. Am. Chem. Soc. 2010, 132 (5), 1508. (19) Lee, S.; Fischer, E.; Czernoak, J.; Nagasundaram, N. J. Alloys Compd. 1993, 197, 1−5. (20) Sugaki, A.; Shima, H.; Kitakaze, A. Synthetic Sulfide Minerals (IV), Technology Report, Yamaguchi University: Yamaguchi, Japan, I, 1972, 76−85. (21) Makovicky, E.; Mumme, W. G.; Watts, J. A. Can. Mineral. 1977, 15, 339−348. (22) CrystalClear, Version 1.3.5; Rigaku Corp.: The Woodlands, TX, 1999. (23) Sheldrick, G. M. SHELXL-97: Program for Crystal Structure Solution; University of Göttingen: Göttingen, Germany, 1997. (24) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7. (25) Kortüm, G. Reflectance Spectroscopy; Springer-Verlag: New York, 1969. (26) Kresse, G.; Furthmüller, J. Comput. Mater. Sci. 1996, 6, 15. 4124


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