a Two-Dimensional Wide-Band-Gap Layered Oxysulfide with Mixed

Communication Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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[(Ba19Cl4)(Ga6Si12O42S8)]: a Two-Dimensional Wide-Band-Gap Layered Oxysulfide with Mixed-Anion Chemical Bonding and Photocurrent Response Yong-Fang Shi,† Xiao-Fang Li,† Yu-Xiao Zhang,†,‡ Hua Lin,*,† Zuju Ma,*,§ Li-Ming Wu,*,⊥ Xin-Tao Wu,† and Qi-Long Zhu*,†

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State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China ‡ University of Chinese Academy of Sciences, Beijing 100049, China § School of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, China ⊥ Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China S Supporting Information *

display interesting crystal color changes from deep-red to yellow based on the [VO4−xSx] BBUs with different O/S ratios.17,18 The Ba6V4O5S11 phase,19 as another unusual example, possesses two types of [VO4−xSx] BBUs simultaneously, i.e., [VO2S2] and [VOS3]. For the latter, the NLO material BaGeSe2O exhibits a remarkable second-harmonic-generation (SHG) efficiency compared to that of the oxide isomorphism as a result of the cooperative arrangement of the highly distorted mixed-anion [GeO2Se2] BBUs.20 Another related example was observed in the polar Mn-doped CaZnOS phase with distorted [ZnOS3] tetrahedra, which shows interesting color manipulation of intense multiluminescence.21 In all of the above-mentioned examples, the heteroligand [MO4−xQx] group is the key structural entity and the M dominantly contains transitionmetal elements, while studies on the group 13 metals (such as Ga3+) are lacking. From the insight of crystallography, four O atoms in the [GaO4] tetrahedron could be replaced by Q atoms at different levels. Namely, the following transformation could be achieved: [GaO4] → [GaO3Q] → [GaO2Q2] → [GaOQ3] → [GaQ4]. In fact, the existing cases of [GaO4−xQx] groups in Ga-containing oxychalcogenides are very rare and limited to only [GaO2Q2]22 and [GaOQ3];23−25 however, there is still no reported example with monosubstitution or even two different types. Recently, we focus on the Ba/MIV/Ga/O/Q/X (MIV = group 14 metal; Q = chalcogen; X = halogen) system and expect to obtain new oxychalcogenides with interesting structures and properties based on the following ideas: (i) the covalent [MO4] and [MQ4] tetrahedra (M = MIV or Ga) are emblematical NLOactive structural BBUs; (ii) the introduction of an X element tends to generate a wide band gap, an important parameter for functional materials such as transparent semiconductors and IR NLO materials. On the basis of these ideas, a novel oxysulfide, [(Ba19Cl4)(Ga6Si12O42S8)] (FJ-1), was discovered in the course of experimental exploration. In this Communication, the solidstate synthesis, crystal structure, and photoelectrochemical

ABSTRACT: Mixed-anion compounds play an essential part in modern structural chemistry. In this Communication, an unprecedented hexanary oxysulfide, [(Ba19Cl4)(Ga6Si12O42S8)] (FJ-1), was synthesized at 1073 K by a standard solid-state method, which is a new phase in the AE/MIII/MIV/O/Q/X (AE = alkaline-earth metal; MIII = group 13 metal; MIV = group 14 metal; Q = chalcogen; X = halogen) system. FJ-1 adopts a new structure type and crystallizes in the orthorhombic system with space group Cmcm. In the structure, unique two-dimensional [Ga6Si12O42S8]34− layers formed by the familiar [SiO4] species and unusual heteroligand [GaO2S2] and [GaO3S] tetrahedra extend the intralayer linking. Significantly, a photoelectrochemical test revealed that FJ-1 is photoresponsive under ultraviolet illumination. Moreover, density functional theory calculations were employed to gain insight into the relationship between the electronic structure and optical properties. Such work will be conducive to the structural diversity of gallium coordination chemistry by exploration of the new mixed-anion functional chalcohalides.

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s new functional materials, mixed-anion inorganic chalcogenides have been receiving widespread attention for their fascinating physical properties, such as nonlinearoptical (NLO) behaviors, thermoelectricity, photoluminescence, superconductivity, magnetism, etc.1−16 Such diverse applications mainly rely on the anionic diversity of these materials. One of the most typical representatives in this field is oxychalcogenides, which contain the different chemical bonding related to oxygen (O) and chalcogen (Q) elements. Although the chemical properties of O2− and Q2− are very different, they usually result in formation of the heteroligand [MO4−xQx] (M = metal cation) basic building units (BBUs) to achieve tunable band-gap engineering or enhanced physical performance. For the former, the classic example is the broad series of isotypic vanadates A3[V(O4−xSx)3] (A = Na, K; x = 0, 1, 2, 3, or 4), which © XXXX American Chemical Society

Received: March 5, 2019

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DOI: 10.1021/acs.inorgchem.9b00653 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 1. Ball-and-stick representation of the unique 2D-layered structure of FJ-1: (a) three BBUs; (b) [Si8Ga6O32S8] cluster formed by different BBUs; (c) disordered [Si2O7] unit; (d) 2D single [Si12Ga6O42S8]34− layer parallel to the b axis; (e) 2D [Si12Ga6O42S8]34− layers stacking along the b direction, with Ba2+ cations and Cl− anions residing in the spaces between the layers; (f) coordination environments of the Ba atoms.

with the charge balanced via the 19 Ba2+ cations and 4 Cl− anions. The key crystallographic parameters of FJ-1 are provided in Tables S1−S3, and there are eight crystallographically independent Ba atoms (Figure 1f), which are bonded with 7− 10 anions with normal Ba−O, Ba−S, and Ba−Cl bond distances, respectively. Colorless crystals were made by solid-state reactions of BaS, BaO, SiO2, Ga2O3, BaCl2, and KCl at 1073 K for 3 days (for details, see the Supporting Information, SI). The powder X-ray diffraction (PXRD) patterns confirm the phase purity of compound FJ-1 (Figure 2a). The experimental energy gap (Eg) of FJ-1 is 4.65 eV according to the UV−vis−near-IR diffuse-reflectance spectrum (Figure 2b). Such a wide band gap is larger than those of many oxysulfides, e.g., Sm3BO3S3 (Eg =

properties of this compound, as well as the relationship between the electronic structure and optical properties, were reported. The result of single-crystal X-ray crystallographic analysis for FJ-1 indicated that it represents a novel structure type and crystallizes in the centrosymmetric orthorhombic system [space group Cmcm (No. 63); Pearson symbol oC388; idealized Wyckoff sequence h19g5f5c]. Compound FJ-1 exhibits a twodimensional (2D)-layered structure consisting of unique [Si8Ga6O32S8] circular groups and [Si2O7] units (Figure 1). In the structure, there are two crystallographiclly unique Ga atoms of which Ga1 (Wyckoff site: 8g) is coordinated to two O and two S atoms and Ga2 (Wyckoff site: 16h) is linked by three O atoms and one S atom. As such, both heteroligand [GaO2S2] and [GaO3S] tetrahedra with typical Ga−O (1.792−1.861 Å)26−28 and Ga−S (2.184−2.203 Å)29−31 distances are formed together (Figure 1a), which is rather uncommon and has never been reported. It is noteworthy that the [GaO3S] species is a newly discovered type of [GaO4−xQx] group in Ga-containing oxychalcogenides. As shown in Figure 1b, two [GaO2S2], four [GaO3S], and four [Si2O7] units apex-shared with each other to build a [Si8Ga6O32S8] circular cluster. These [Si8Ga6O32S8] clusters connect to bond a 2D wavelike layer, [Si12Ga6O42S8]34− (Figure 1d, dashed area), along the ac plane through a disordered [Si2O7] unit, sharing corners with O9 atoms (Figure 1c). Discrete Ba2+ cations and Cl− anions fill in the spaces between these layers (Figure 1e). In terms of connectivity, the structure of 1 may be described as {4[Si1O2O2/2]2−4[Si2OO3/2]−4[Si3O2O2/2]2−2[Ga1OS2]4−4[Ga2O3/2S]−}34−

Figure 2. Property measurements for FJ-1: (a) experimental (black) and calculated (red) PXRD patterns; (b) UV−vis diffuse-reflectance spectrum. B

DOI: 10.1021/acs.inorgchem.9b00653 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry 2.50 eV),32 Na6Si3S8O (Eg = 3.57 eV),33 and Ba2In2Si3O10S (Eg = 4.46 eV).34 To investigate the optical behavior of FJ-1, a photoelectrochemical cell consisting of three electrodes was constructed (detailed information is given in the SI), and the result of the transient photocurrent was recorded. As shown in Figure 3a, an obvious photocurrent was generated when the FJ-

state. Group V from 7.5 to 12 eV mainly consists of Ga 4p−O 2p, Ga 4p−S 3p, and Si 3p−O 2p antibonding states. Figure 4b shows the calculated frequency-dependent total absorption coefficient spectrum of FJ-1. We attempt to identify the band transitions that are responsible for the spectral character using our calculated electronic structure. The transitions from group III to group IV are responsible for the first peak around 11 eV in the absorption spectra and the transitions from group II to group V for the second peak around 19 eV. Therefore, the interband transitions from the Ga 4p, O 2p, Si 3p, and S 3p orbitals to the Ba 5d unoccupied orbital contribute to absorption in the energy range 9−13 eV, while the transitions from the Ga 4s, Si 3s, and O 2p orbitals to the Ga 4p, O 2p, Si 3p, and S 3p unoccupied orbitals are responsible for absorption for the energies around 19 eV. In summary, a new oxysulfide, FJ-1, of the type AE/MIII/MIV/ O/Q/X (AE = alkaline-earth metal; MIII = group 13 metal; MIV = group 14 metal; Q = chalcogen; X = halogen) has been obtained through a solid-state reaction in the sealed system. It represents a novel structure type, and the overall structure consists of different building units, including commonly [SiO4] species and unusual heteroligand [GaO2S2] and [GaO3S] tetrahedra, which are connected to each other through vertex sharing in a wavelike fashion along the b axis to form infinite 2D [Ga6Si12O42S8]34− layers and separated by isolated Ba2+ cations and Cl− anions. FJ-1 shows an indirect Eg value of 4.65 eV and exhibits interesting photoelectric properties. A DFT study, in particular the DOS, illustrated that optical absorption of FJ-1 mainly originates from the 2D [Ga6Si12O42S8]34− layer. Such work not only enriches the gallium coordination chemistry but also facilitates the design and synthesis of new mixed-anion functional chalcohalides.

Figure 3. (a) Transient photocurrent response of FJ-1 under 4 W ultraviolet irradiation with a wavelength centered at 254 nm in a 0.1 mol/L Na2SO4 solution. (b) Mott−Schottky and current−potential plots (in the inset) of FJ-1.

1-based photoelectrochemical cell was subjected to excitation with ultraviolet light. Moreover, the reproducibility of the transient photocurrent response was confirmed by the on−off cycles of illumination. According to the Mott−Schottky plots shown in Figure 3b, the positive slope value indicates that FJ-1 is an n-type semiconductor,35 which was further confirmed by the increasing anodic photocurrent with increasing applied potential in the inset. We next investigated the title compound utilizing density functional theory (DFT) calculations to gain a better understanding of the relationship between the electronic structure and optical properties. Figure S4 depicts the electronic band structure of FJ-1 calculated at the Perdew−Burke−Ernzerhof (PBE) level.36 FJ-1 shows an indirect Eg value of 3.52 eV. Such a value is smaller than the experimental gap (Eg = 4.68 eV), as was expected from the underestimation of the PBE calculation.37 Furthermore, the projected densities of states (PDOSs) are represented in Figure 4a. To identify the angular momentum

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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.9b00653. Synthesis, property characterization, and computational section (PDF) Accession Codes

CCDC 1890910 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Figure 4. Calculated (a) PDOSs and (b) total absorption coefficient spectra of FJ-1. The Fermi level EF is set at 0 eV.

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected].

origin of the Eg region, we can divide the PDOSs into five groups. The lowest energy from −13 to −10 eV (group I) is dominated by the Ba 5p state and the Ga 4s−S 3s bonding state. The group II from −10 to −7 eV has significant contributions from Ga 4s− O 2p and Si 3s−O 2p bonding states. The top of valence bands ranging from −7 to 0 eV (group III) are mainly composed of Ga 4p−O 2p, Ga 4p−S 3p, and Si 3p−O 2p bonding states and a Cl 3p nonbonding state. The lowest conduction bands between 3.5 and 7.5 eV (group IV) has mainly been derived from the Ba 5d

ORCID

Hua Lin: 0000-0002-7241-9623 Li-Ming Wu: 0000-0001-8390-2138 Qi-Long Zhu: 0000-0001-9956-8517 Notes

The authors declare no competing financial interest. C

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ACKNOWLEDGMENTS This research was supported by the National Natural Science Foundation of China (Grants 21771179, 21771182, 21501177, 21571020, and 21301175), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20010200), the “Chunmiao Projects” of Haixi Institute of Chinese Academy of Sciences, Natural Science Foundation of Fujian Province (Project 2019J01133), and the One Thousand Young Talents Program under the Recruitment Program of Global Youth Experts.

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