Designing and tuning properties of a three-dimensional porous quaternary chalcogenide built on a bimetallic tetrahedral cluster [M4Sn3S13]5− (M=Zn/Sn)

doi:10.1016/j.jssc.2007.12.035

Journal of Solid State Chemistry

Volume 181, Issue 3, March 2008, Pages 415-422

https://doi.org/10.1016/j.jssc.2007.12.035 Get rights and content

Abstract

A multifunctional three-dimensional quaternary chalcogenide [Na₅Zn_3.5Sn_3.5S₁₃]·6H₂O has been synthesized by solvothermal reactions. [Na₅Zn_3.5Sn_3.5S₁₃]·6H₂O represents an interesting example of metal chalcogenides that combines semiconductivity, porosity, and light emission in a single structure. It crystallizes in the cubic space group Fm-3c, a=17.8630(3) Å, V=5699.85(17) Å³, Z=8. The compound decomposes at ∼450 °C. A band gap of 2.9 eV is estimated from the optical diffuse reflectance data. A strong photoluminescence peak is observed at 2.43 eV in Mn doped samples. The electronic and optical properties of this compound can be systematically tuned by substitution of metal and chalcogen elements.

Graphical abstract

A three-dimensional quaternary chalcogenide [Na₅Zn_3.5Sn_3.5S₁₃]·6H₂O represents an interesting example of chalcogenide based semiconductor that combines semiconductivity, porosity, and light emission in a single structure. The electronic and optical properties of this compound can be systematically tuned by substitution of metal and chalcogen elements.

Introduction

Solid state metal chalcogenide materials have attracted considerable attention because of their superior semiconductor properties that can be used in numerous commercial applications, such as sensors, solar cells, solid electrolytes, and lasers [1], [2], [3], [4]. Strong interests are generated recently in the design and synthesis of open-framework chalcogenides, in attempts of developing multifunctional materials that are capable of integrating porosity, electronic and optical properties in a single crystal structure and thus, hold promise for potential utility in areas such as catalysis, sorption, ion exchange, and gas storage, in addition to their useful optoelectronic properties. Design and understanding metal chalcogenide clusters can be very helpful for the development of porous chalcogenides, since many three-dimensional chalcogenides are constructed from these clusters. Some good examples of tetrahedral metal chalcogenide clusters have been reported for Groups 13–15 and transition metal elements [5].

A number of open-framework metal chalcogenides have been previously synthesized [5], [6], [7], [8]. Most of these compounds are built upon regular supertetrahedral clusters Tn (Mt_nQt_n₊₁, M=metal, Q=S, Se, Te, t_n=n(n+1)(n+2)/6, n⩾1) [6], or penta-supertetrahedral clusters Pn ((Mt_nQt_n₊₁)₄(Qt_nMt_n₊₁) (n⩾1)) [9]. These two common building units have the same geometrical features and follow the same construction rules. Single metal cations, or bimetallic cations in these supertetrahedral clusters are usually M²⁺, M³⁺, M⁴⁺, [M⁴⁺–M³⁺] for T2, T3, and T4; [M⁺–M³⁺], [M²⁺–M³⁺] for T4, T5, and P2 (M=Cu⁺, Zn²⁺, Fe²⁺, Co²⁺, In³⁺, Ga³⁺, Sn⁴⁺, Ge⁴⁺, etc.) [9], [10], [11], [12], [13], [14].

[M²⁺–M⁴⁺] chalcogenides are semiconductors containing a divalent (M²⁺) transition metal chalcogenide and a tetravalent (M⁴⁺) metal [15]. P1 (or partially distorted P1) and T3 cluster types for this combination have been reported [8], [15], [16], [17], [18]. While metal chalcogenides built upon supertetrahedral clusters have been investigated quite extensively, relatively little progress has been made on compounds made of other types of tetrahedral clusters. Here we report an open-framework three-dimensional quaternary chalcogenide compound [Na₅Zn_3.5Sn_3.5S₁₃]·6H₂O (1) that is constructed on a unique bimetallic tetrahedral cluster with systematically tunable properties.

Section snippets

Crystal growth and sample preparation

Single crystals of [Na₅Zn_3.5Sn_3.5S₁₃]·6H₂O (1) were obtained in a reaction containing 0.50 mmol of Na₂S, 0.80 mmol of S, 0.25 mmol of Sn, and 0.017 mmol of ZnCl₂. The starting materials were pre-mixed and grinded, and then loaded in a 9 mm OD thick wall Pyrex tube. The sample was pre-heated at 90 °C for 1 h and followed by addition of 0.20 mL CH₃OH and 0.20 mL H₂O. The reaction was heated at 150 °C for 7 days. The products were washed with 80% alcohol followed by water. Pale yellow cubic crystals and

Results and discussion

The building block of the three-dimensional [Na₅Zn_3.5Sn_3.5S₁₃]·6H₂O (1) structure is a bimetallic cluster [M₄Sn₃S₁₃]⁵⁻, which consists of four MS₄ (M=0.125Sn+0.875Zn) tetrahedra that share a corner of S atom at the core, and $6 \times \frac{1}{2}$ terminal SnS₄ tetrahedra. Two of the S atoms in each SnS₄ tetrahedron are corner-shared with two MS₄ tetrahedra within the same cluster while the other two S atoms link to two MS₄ tetrahedra in the adjacent cluster by corner-sharing. The building block can also be

Concluding remarks

In summary, a new open-framework quaternary metal chalcogenide compound [Na₅Zn_3.5Sn_3.5S₁₃]·6H₂O built on an bimetallic tetrahedral cluster [M₄Sn₃S₁₃]⁵⁻ (M=0.125Sn+0.875Zn), has been synthesized and characterized. The compound combines semiconductor properties with other interesting functionality such as porosity in a single structure. The successful doping/substitution of Mn and Se allows systematic tuning of the band gap and optical properties of this semiconductor compound. The relatively

Acknowledgments

We are grateful to the National Science Foundation for the generous support of this research through Grant DMR-0422932. Work at NREL was supported by NREL LDRD (#06590504).

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Journal of Solid State Chemistry

Abstract

Graphical abstract

Introduction

Section snippets

Crystal growth and sample preparation

Results and discussion

Concluding remarks

Acknowledgments

References (24)

Mater. Res. Bull.

Solid-State Electron.

Jpn. J. Appl. Phys. Part 1—Regular Papers Short Notes & Review Papers

Opt. Rev.

Science

Science

Chemistry—a Eur. J.

Science

J. Am. Chem. Soc.

Chem. Commun.

Angew. Chem.—Int. Ed.

J. Am. Chem. Soc.

Cited by (32)

Ternary 3D framework [Ag<inf>5</inf>Sn<inf>4</inf>Se<inf>12</inf>]<sup>3−</sup>: Solvothermal synthesis, crystal structure and photoelectric properties of an organic silver-rich selenidostannate hybrid

Na/Zn/Sn/S (NaZTS): Quaternary metal sulfide nanosheets for efficient adsorption of radioactive strontium ions

T3 supertetrahedral cluster [Mn<inf>4</inf>Sn<inf>6</inf>S<inf>20</inf>]<sup>8−</sup>: Solvothermal syntheses, crystal structures and photocatalytic properties of Mn(II) chalcogenidostannates

Synthesis, crystal structure, and optical property of a one-dimensional selenidostannate: [AEPPH<inf>2</inf>]<inf>2</inf>[Sn<inf>5</inf>Se<inf>12</inf>] (AEPP = N-aminoethylpiperazine)

Complexations of Ln(III) with SnS<inf>4</inf>H and Sn<inf>2</inf>S<inf>6</inf>: Solvothermal syntheses and characterizations of lanthanide coordination polymers with thiostannate and polyamine mixed ligands

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