An open-framework bimetallic chalcogenide structure K3Rb3Zn4Sn3Se13 built on a unique [Zn4Sn3Se16]12− cluster: synthesis, crystal structure, ion exchange and optical properties

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Abstract

Single crystals of K3Rb3Zn4Sn3Se13 were synthesized by solvothermal method. The building block in this structure is a [Zn4Sn3Se16]12− cluster which consists of four ZnSe4 and three SnSe4 tetrahedra connected through corner-sharing of Se atoms. The 3D network contains intersecting channels running parallel to the crystallographic [2 1 1], [1-1-1] and [12-1] directions. The disordered K+ and Rb+ cations reside in these channels. Ion exchange of Cs+ with disordered Rb+/K+ ions in the structure showed a partial replacement of 15.8%. Optical diffuse reflectance experiments were carried out and gave a sharp absorption edge at 2.6 eV.

Introduction

Considerable efforts have been made to synthesize open framework metal chalcogenides as multifunctional materials in combination of their porosity and optoelectronic properties [1], [2], [3], [4], [5], [6]. However, until recently, preparation of chalcogenide analogues of oxide porous materials such as zeolites remains a challenge due to the fact that metal chalcogenides tend to form close-packed structures instead of open frameworks of low density, as a result of the relatively small binding angles at chalcogen atoms. An important strategy, proposed to lift this limitation, is to employ molecular clusters as secondary building blocks to generate open framework structures [7]. Application of this synthetic approach has resulted in some promising results. For example, several very open frameworks of indium sulfides have been achieved by condensation of [In10S20]12− clusters [8]. Recently, a series of indium (gallium) sulfides composed of chalocogenide supertertrahedral clusters have been reported [9], [10], [11], [12]. Since the shape and size of the pores within the open framework structures are defined by these clusters, and the number and types of clusters are, in principle, unlimited, such a synthetic approach is highly promising for generating porous materials in general. Use of surfactant cations as structure directing regents has also led to the formation of a series of microporous metal germanium chalcongenides assembled from adamantane-like [Ge4Q10]4− clusters (Q = S, Se) with metal ions (Mn2+, Ag+, Fe2+, Ni2+, Zn2+, Co2+, Cu22+, Hg2+, Ga3+, In3+) [13], [14], [15], [16], [17], [18], [19], [20], [21]. Fig. 1 shows several cluster units that we have found in chalcogenide structures, including (a) semi-cube [M3Q7]2− [22], (b) adamantane-like [M4Q10]4−, (c) [M3Q7]3− [23], and (d) [M5Q9]3− [24]. While tin chalcogenide frameworks composed of primary building block, e.g., tetrahedral [SnQ4]4− (Q = S, Se, Te) unit, have been well documented [1], [2], very few open frameworks assembled from bimetallic clusters incorporating [SnQ4]4− and another metal species [25], [26], [27]. In this article, we report a three dimensional open framework structure based on a secondary building block, the [Zn4Sn3Se16]12− cluster.

Section snippets

Experimental

Single crystals of K3Rb3Zn4Sn3Se13 (1) were grown in a reaction containing 0.079 g (0.5 mmol) of K2Se, 0.0495 g (0.6 mmol) of Se, 0.030 g (0.25 mmol) of Sn, 0.060 g (0.5 mmol) of RbCl and 0.023 g (0.017 mmol) of ZnCl2 loaded in thick wall Pyrex tube, followed by addition of 0.2 ml H2O and 0.2 ml CH3OH. The reaction mixture sealed in tube was heated at 130 °C for 6 days. The product was washed with 80% alcohol followed by water and pure yellow crystals obtained with ca. 60% yield.

Powder X-ray diffraction

Results and discussion

Single crystal X-ray diffraction studies revealed that the title compound is a three dimensional structure. Crystal data for compound 1: space group R3m (no. 160), a = 14.650(2) Å, c = 15.744(3) Å, V = 2926.0(3) Å3, Z = 3, dcalcd = 3.435 g cm−3, μ (Mo Kα) = 20.468 mm−1. The basic building block in this structure is a [Zn4Sn3Se16]12− cluster which consists of four ZnSe4 and three SnSe4 tetrahedra connected through corner-sharing of Se atoms as shown in Fig. 2a. The [Zn4Sn3Se16]12− cluster possesses a C3V symmetry

Conclusions

In summary, open-framework bimetallic chalcogenide compounds can combine semiconductor properties with other interesting functionality such as porosity in a single structure. There is a great potential to develop and to tailor these materials based on desired multifunctionality. Future investigation will focus on the design and synthesis of chalcogenides that make use of both electron charge and spin and are potentially important in optoelectronic devices and information storage.

Acknowledgements

The support from the National Science Foundation (Grant DMR-0094872) is gratefully acknowledged.

References (27)

  • W.S. Sheldrick et al.

    Angew. Chem. Int. Ed. Engl.

    (1997)
  • W.S. Sheldrick

    J. Chem. Soc., Dalton. Trans.

    (2000)
  • S. Dhingra et al.

    Science

    (1992)
  • J.B. Parise

    Science

    (1991)
  • K.W. Kim et al.

    J. Am. Chem. Soc.

    (1992)
  • H. Ahari et al.

    J. Chem. Soc., Dalton Trans.

    (1998)
  • H. Li et al.

    Science

    (1999)
  • H. Li et al.

    J. Am. Chem. Soc.

    (1999)
  • W.P. Su et al.

    J. Am. Chem. Soc.

    (2002)
  • X. Bu et al.

    J. Am. Chem. Soc.

    (2002)
  • X. Bu et al.

    J. Am. Chem. Soc.

    (2003)
  • N. Zheng et al.

    J. Am. Chem. Soc.

    (2003)
  • O.M. Yaghi et al.

    J. Am. Chem. Soc.

    (1994)
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    Present address: Department of Chemistry, Iowa State University, Ames, IA 50011, USA.

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