[CH3NH3]2Ag4SnIV2SnIIS8: An Open-Framework Mixed-Valent

Synopsis. Presented is the first organically templated three-dimensional Ag−Sn−S compound containing the mixed valence of Sn(IV)/Sn(II), namely [C...
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[CH3NH3]2Ag4SnIV2SnIIS8: An Open-Framework Mixed-Valent Chalcogenidostannate Bo Zhang,†,‡ Jun Li,†,‡ Cheng-Feng Du,† Mei-Ling Feng,† and Xiao-Ying Huang*,† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People’s Republic of China ‡ University of Chinese Academy of Sciences, Beijing, 100049, People’s Republic of China S Supporting Information *

photocatalytic degradation activity over crystal violet (CV) under visible light irradiation. The orange needle-shaped crystals of 1 were obtained through a solvothermal reaction of AgCl, Sn, S, and methylamine (33−40% alcohol solution) at 160 °C for 8 days. Single crystal X-ray diffraction analysis revealed that compound 1 belongs to the orthorhombic space group of Pnma (No. 62) with half a formula unit in the crystallographically asymmetric unit. Its structure is characterized by a 3D anionic open framework of [Ag4SnIV2SnIIS8]n2n− with one-dimensional (1D) channels along the b axis where the methylamine [CH3NH3]+ cations as structure-directing agents or templates reside, Figure 1. The asymmetric unit of 1 contains two unique Ag(I) ions (Ag(1) and Ag(2)), two halves of Sn(IV) ions ((Sn(1) and Sn(3)), half a Sn(II) ion (Sn(2)), two and four halves of S2− ions, and two halves of [CH3NH3]+ cations. Except for Ag(1), Ag(2), S(2), and S(6), all the non-hydrogen atoms are located at 4c sites with mirror symmetry. The Ag(1) atom is in a trigonal environment bonding to three S atoms, while Ag(2) is in a distorted tetrahedral coordination geometry with four S atoms. The Sn(1) and Sn(3) atoms are tetrahedrally coordinated by four S atoms, while the Sn(2) atoms adopt an infrequent trigonal pyramidal coordination geometry (Figure S2). In the pyramidal [Sn(2)S3] unit, the Sn(2)−S distances and S−Sn(2)−S angles fall in the range of 2.5193(19)−2.5676(14) Å and 86.47(6)−94.07(4)°, respectively, which are comparable with those in BaSnIIS2,21 BaSnII2S3,22 BaSnII3S4,23 Ba7SnIV3SnII2S15,14 BaLnSnIV1.5SnII0.5S6 (Ln = Ce, Pr, Nd),17 [DBNH]2SnIV2SnIIS6,18 (enH)3Cu7SnIV3SnIIS12, and (trenH3)Cu7SnIV3SnIIS12.19 Vertex-sharing of two [Ag(1)S3] and two [Ag(2)S4] units produces an eight-membered [Ag4S4] ring; such rings are interconnected via corner-sharing S(1) and S(3) atoms to constitute a 1D [Ag4S7]n10n− ribbon extending along the b axis (Figure 1a). The [SnIVSnIIS5]n4n− chain is formed by alternating arrangement of [Sn(2)S3] pyramids and [Sn(1)S4] tetrahedra via vertex-sharing S(2) atoms along the b axis (Figure 1b). Then, the [Ag4S7]n10n− ribbon and the [SnIVSnIIS5]n4n− chain are condensed by sharing the S(1) and S(3) atoms to give rise to a [Ag4SnIVSnIIS8]n6n− ribbon (Figure 1c). Such two centrosymmetric [Ag4SnIVSnIIS8]n6n− ribbons are further fused via sharing the S(1) atoms to form a complex [Ag4SnIVSnIIS8]n6n− ribbon extending along the b axis (Figure

ABSTRACT: An open-framework chalcogenidostannate, namely, [CH3NH3]2Ag4SnIV2SnIIS8 (1), has been solvothermally synthesized and structurally characterized, which represents the first organically templated three-dimensional (3D) Ag−Sn−S compound containing the mixed valence of Sn(IV)/Sn(II) and displays visible-light-driven photocatalytic activity for degradation of crystal violet (CV).

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halcogenidostannates continue to fascinate researchers by virtue of their attractive architectures and great potentials in the fields of ion exchange,1 photocatalysis,2 fast-ion conduction,3 nonlinear optics,4 and so on. Their structures and properties can further be enriched through incorporating second or even third types of metal ions (e.g., Ag+, Cu+, Zn2+) forming Sn-based multinary chalcogenidometalates.1a,c,5 Meanwhile, the chalcogenidometalates with a mixed valence6−19 have received considerable attention due to their unique properties and promising applications in superconductivity,7 metallic conductivity,8 charge-density waves,9 and magnetism.10 However, hitherto the mixed-valent chalcogenidostannates(II,IV) have rarely been isolated. The limited examples mainly focus on inorganic compounds, such as K 2 Sn IV 3 Sn II Se 8 , 11 K 2 Sn IV Sn II Se 4 , 12 Rb 2 Sn IV 3 Sn II Se 8 , 13 Ba7SnIV3SnII2S15,14 Ba6SnIVSnII5Se13,15 SrSnIVSnIISe4,16 and BaLnSnIV1.5SnII0.5Q6 (Ln = Ce, Pr, Nd, Q = S; Ln = Ce, Q = Se),17 which normally were prepared via high-temperature solid state or intermediate-temperature flux techniques. The organically templated examples are [DBNH] 2 SnIV 2SnIIS 6 (DBN = 1,5-diazabicyclo[4.3.0]non-7-ene),18 (enH)3Cu7SnIV3SnIIS12 (en = ethylenediamine), and (trenH3)Cu7SnIV3SnIIS12 (tren = tris(2-aminoethyl)-amine).19 Indeed, the mild solvothermal techniques have proven to be effective for the preparation of novel chalcogenidometalates.20 To our knowledge, however, there is no report of solvothermal preparation of organically templated Ag−Sn−Q (Q = S, Se, Te) compounds containing mixed-valent Sn(IV)/Sn(II). In this communication, we report on the solvothermal synthesis, crystal structure, and optical property of a novel methylamine-directed Ag−Sn−S compound, namely, [CH3NH3]2Ag4SnIV2SnIIS8 (1). Compound 1 possesses a three-dimensional (3D) open-framework structure and represents the first Ag−Sn−S compound characteristic of a mixed valence of Sn(IV) and Sn(II). Interestingly, 1 showed © XXXX American Chemical Society

Received: September 23, 2016

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DOI: 10.1021/acs.inorgchem.6b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

Figure 2. (a) Sn 3d peak in the XPS spectrum of compound 1. (b) The calculated partial density of states for Sn(II) and Sn(IV) in 1. The Fermi level (dashed line) is set at 0 eV. (c) Electron density difference diagram for compound 1 from a view of the [0 1 0] plane containing Sn(IV) and Sn(II) ions. The red and blue areas represent electron accumulation and depletion, respectively. (d) The partial charge density (in unit of electrons per Å3) plots corresponding to the conduction bands minimum (light green isosurface) of 1 with an isovalue of 0.0025 e Å−3. Figure 1. (a) [Ag4S7]n10n− ribbon where the [Ag4S4] rings are filled in green. (b) [SnIVSnII S 5 ]n 4n− chain. (c) Two centrosymmetric [Ag4SnIVSnIIS8]n6n− ribbons. (d) [Ag4SnIVSnIIS8]n6n− ribbon. (e) [Sn(3)S4] tetrahedron. (f) Perspective view of the open-framework structure of compound 1 along the b axis with one of the [Ag4SnIVSnIIS8]n6n− ribbons circled. C, N, and H atoms are omitted for clarity.

Differently, in the upper panel, Sn 5p orbitals dominate the states above the Fermi level, and the states below Fermi level are mainly made up of 5s characters, which contribute to the Sn(II) configuration. Moreover, the two characteristics of Sn atoms can also be reflected in the electron density difference (Figure 2c) and conduction-electron charge density (Figure 2d). The unequal electron density distribution around Sn(IV) and Sn(II) regions further confirmed the experimental results and the above theoretical analyses. The solid-state UV−vis absorption spectrum revealed that the optical band gap of compound 1 is 2.10 eV (Figure 3a),

1d). Each [Ag4SnIVSnIIS8]n6n− ribbon further connects four adjacent [Ag4SnIVSnIIS8]n6n− ribbons via tetrahedral Sn(3)4+ ions (Figure 1e) to result in the final 3D anionic openframework structure of [Ag4SnIV2SnIIS8]n2n− with 1D channels (Figure 1f). The free volume in 1 excluding the organic cations is about 22.2% calculated by PLATON.24 An intriguing structural feature of compound 1 is that there exists mixed-valent Sn atoms in the ratio of Sn(II)/Sn(IV) = 1/ 2. Such assignment can be confirmed by the valence sums 4.585, 2.285, and 4.609 for Sn(1), Sn(2), and Sn(3), respectively, calculated by using Brown’s bond-valence model.25 X-ray photoelectron spectroscopy (Figure 2a) analysis showed the presence of two different binding energies of each peak (486.0 and 486.6 eV; 494.5 and 495.0 eV), which can be assigned respectively to Sn(II) and Sn(IV) oxidation states.26 Furthermore, the Sn(II)/Sn(IV) atomic ratio calculated from the area of the XPS peaks is 1/2.1, which agrees well with that obtained from the single crystal data refinement and bondvalence calculation. To further reveal the native valence sates of Sn atoms in compound 1, theoretical calculations based on density functional theory (DFT) were performed. The Mulliken population analysis27 showed that Sn atoms hold two kinds of positive charges, namely, 0.72 and 1.02 e, suggesting two valence states assigned to Sn. The partial density of states of two kinds of Sn atoms was displayed in Figure 2b. In the lower panel, the conduction bands (CBs) close to the Fermi level are mainly made up of Sn 5s states, indicating electrons from both 5s and 5p orbitals transferred from valence bands (VBs) to conduction bands (CBs), giving the Sn(IV) configuration.

Figure 3. (a) Solid-state UV−vis absorption spectrum of compound 1. (b) Photodegradation of CV by 1 monitored as the normalized change in concentration as a function of irradiation time.

which lies in the energy range suitable for visible-light photocatalytic applications. This value is comparable to those of other Ag−Sn−Q (Q = S, Se) compounds, such as [enH2]Ag2SnS4 (2.20 eV),28 [Hen]4[Ln(en)4]2[Ag6Sn6S20]· 3en (Ln = Er, 2.18 eV; Tm, 2.39 eV; Yb, 2.47 eV),29 K2Ag6Sn3S10 (1.80 eV),5a [Bmmim]7[AgSn12Se28] (2.20 eV, Bmmim = 1-butyl-2,3-dimethyl-imidazolium),30 [(Me)2NH2]3[Ag5Sn4Se12] (1.85 eV),5b K2Ag2SnSe4 (1.80 eV),31 and Rb3AgSn3Se8 (1.80 eV).32 Recently, the photocatalytic degradation of organic pollutants by semiconductors for wastewater purification has triggered considerable attention.33 Crystal violet (CV), which is found to B

DOI: 10.1021/acs.inorgchem.6b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry be a highly cytotoxic and refractory fluorescein dye for humans, was selected as a model pollutant to examine the visible-light photocatalytic activity of compound 1. The characteristic absorption of CV at about 589 nm was selected for monitoring the adsorption and photocatalytic degradation process. The degradation efficiency is defined as C/C0, where C and C0 represent the remnant and initial concentration of the organic dye. As presented in Figure 3b, the photolysis of CV without the photocatalyst could be neglected. After 200 min of photoreaction, the degradation ratio of CV reached 92%. The degradation efficiency of compound 1 over CV is comparable with that of some metal oxides and halides.34 In addition, XRD characterization shows that there is no obvious change before and after the photocatalytic process, demonstrating the stability of 1 as the catalyst (Figure S10). We attribute the high photocatalytic efficiency and high stability to a suitable energy band gap corresponding to absorption of visible light coupled with high stability of the skeleton structure of chalcogenidometalates. In summary, a novel methylamine-directed Ag−Sn−S compound has been solvothermally synthesized and structurally characterized. Compound 1 represents the first 3D Ag− Sn(IV)/Sn(II)−S compound. Compound 1 exhibited the ability of photocatalytic degradation of CV under visible light irradiation. This work demonstrates that the solvothermal method is applicable to the synthesis of mixed-valent chalcogenidostannates. Future studies will be focused on the exploratory synthesis of more organically templated functional M−Sn−Q compounds containing mixed-valent Sn(IV)/Sn(II) and a deep understanding of the relationship between structure and property.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b02317. More structural details and figures, powder X-ray diffraction patterns, EDS and DFT calculation results (PDF) Crystallographic information for compound 1 (CIF) Accession Codes

CCDC No. 1503285 (1) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the NNSF of China (Nos. 21521061 and 21373223) and 973 program (No. 2014CB845603). We acknowledge the Supercomputing Center of CNIC for providing the computer resources.

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REFERENCES

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DOI: 10.1021/acs.inorgchem.6b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.6b02317 Inorg. Chem. XXXX, XXX, XXX−XXX