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Solvothermal syntheses and structures of A3AgSn3Se8 (A = Rb, K)
Inorganic Chemistry Communications 10 (2007) 555–557 www.elsevier.com/locate/inoche
Solvothermal syntheses and structures of A3AgSn3Se8 (A = Rb, K) Min Ji a, Menghe Baiyin a, Shouhua Ji b, Yonglin An a
a,*
Department of Chemistry, Dalian University of Technology, Dalian 116024, China Department of Materials, Dalian University of Technology, Dalian116024,China
b
Received 3 December 2006; accepted 24 January 2007 Available online 2 February 2007
Abstract Two new compounds A3AgSn3Se8(A = K, Rb) were synthesized solvothermally and characterized by X-ray single crystal diffraction. These compound are composed of building block [Sn3Se8]4 formed by three edge-sharing SnSe4 tetrahedra, and these building blocks are further connected by tetrahedral coordinated Ag+ to form infinite chains, alkali cations are located between the chains. Their optical properties were also studied. 2007 Elsevier B.V. All rights reserved. Keywords: Solvothermal synthesis; Quaternary selenostannate; Chains structure; Optical properties
In the past decades, syntheses of chalcogenides have received much attention in solid state chemistry and material sciences [1]. Many binary and ternary chalcogenides with interesting structures have been synthesized by various techniques [2,3]. Compared with binary and ternary chalcogenides, the quantity of known quaternary chalcogenides is much less, and quaternary chalcogenides usually were prepared by molten alkali-metal polychalcogenide flux or high-temperature solid state techniques [4–9]. In contrast to chalcogenides prepared hydro(solvo)thermally, most of the high-temperature quaternary phases contain relatively simple building blocks because molecular building blocks such as chains or rings can’t remain to participate in the formation of interesting structures under the high temperature conditions. From the structural point of view, quaternary chalcogenides have more complex structures and interesting properties than binary or ternary ones do due to the complex composition and combination of various structural building blocks. In principle, mild hydro(solvo)thermal method should be an effective route to access new quaternary chacogenides. Under relatively mild conditions, the molecular building blocks can be *
Corresponding author. E-mail address: [email protected] (Y. An).
1387-7003/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2007.01.023
assembled to a fascinating variety of quaternary chacolgenides. However solvothermal synthesis has produced a limited number of quaternary chalcogenides up to now [10– 14]. To some extent, this situation results from deficient research on mineralizers for the synthesis. In spite of some synthetic strategies such as usage of supercritical conditions have been developed [15], lack of effective mineralizers retards successful hydro(solvo)thermal synthesis of quaternary chacogenides. Recently, our exploratory research has demonstrated that HSCH2CH(SH)CH2OH is a very good mineralizer for solvothermal synthesis of various sulfides [16]. With an aim of searching for an effective mineralizer, we carried out the investigation on solvothermal synthesis of quaternary selenostannate [16]. In this publication, we report a solvothermal synthesis of two novel quaternary selenostannate in the presence of glycol. The synthesis of Rb3AgSn3Se8 (1) was as follows: 0.010 g of powder Ag , 0.060 g of Sn, 0.060 g of powder Se, and 0.120 g of Rb2CO3 were put into a Pyrex glass tube, to which 0.6 mL of pyridine/glycol = 2:1 was added. The glass tube was sealed with a 10% filling, placed into a Teflon-lined stainless steel autoclave, and heated at 180 C for 7 days. The products were washed with ethanol and water, respectively, pure red crystals were obtained with a 70% yield based on silver. A composition analysis
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M. Ji et al. / Inorganic Chemistry Communications 10 (2007) 555–557
by an energy-dispersive spectrum collected by a scanning electron microscope indicated the presence of Se, Rb, Ag, and Sn in a 54.20:17.63:7.21:20.96 molar ratio, which is consistent with that expected from the following crystal structure determination. By the above method, a pure compound K3AgSn3Se8 (2) was also obtained. Our research showed that glycol is essential for the synthesis, the effect of glycol may result from the formation of some selenoglycol , which can play a role of the mineralizer. Crystal structure analysis showed that compounds 1 and 2 are isostructural, consisted of linear building block Sn3 Se4 8 , in which three tetrahedral SnSe4 share their edges [17]. These building blocks Sn3 Se4 8 are further connected by Ag+ ions to form infinite single chains as shown in Fig. 1. Each chain has a C2 rotational symmetry along the c direction, and the adjacent chain has different tetrahedral orientation as seen in Fig. 2. The rotational symmetry of the chains result in each tetrahedral AgSe4 and the middle SnS4 of Sn3 Se4 have only one kind of bond 8 lengths, and two side SnSe4 tetrahedra are identical, and with two kind of bond lengths, and terminal Sn–Se of Sn3 Se4 is longer than bridging Sn–Se. In compound 1, 8 the middle SnSe4 of Sn3 Se4 has the bond length of 8 ˚ for its four Sn–Se bonds and bond angles Se–Sn– 2.515 A
Fig. 1. A single chain ½AgSn3 Se3 3 1 of compound 2 showing the C2 symmetry along c direction and linkage between the building unit [Sn3Se8]4 and Ag+. Grey, Sn; blue, Ag; brown, Se. (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. The adjacent chains with different tetrahedral orientations in the compound 2. Grey tetrahedra, SnSe4; blue tetraheda, AgSe4. (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
Se between 97.39 and 115.83, the side tetrahedral SnSe4 are distorted slightly with the bond length of Sn–Se ˚ and 2.620 A ˚ , respectively, and bond angles Se– 2.473 A Sn–Se in the range of 92.30–112.92. The tetrahedral AgSe4 ˚ , and bond angles Se–Ag– have the bond length of 2.794 A Se 95.11–117.09. In compound 2, the middle tetrahedral ˚ and bond angles SnSe4 has the bond length of 2.521 A Se–Sn–Se between 97.41 and 115.82. For the side tetrahe˚ and 2.616 A ˚, dral SnSe4, the bond lengths are 2.478 A respectively, and the bond angles in the range of 92.74– 112.47. The tetrahedral AgSe4 have the bond length of ˚ and bond angles 96.23–116.47. From above com2.771 A parison, it can be seen that alkali cations located between anionic chains have a little effect on the bond lengths and angles of tetrahedra in the chain, indicating the covalent nature of the bonding in the chain (see Fig. 3). The linkage of tetrahedral Sn and Ag in compounds 1 and 2 is the same as that in the structure of SiS2, in which tetrahedral SiS4 shares their edges to form a single chain [18]. This kind of linkage also implies the strong covalent characteristics of these compounds. Krebs and co-workers showed that various tetrahedral selenostannate anions exist in alkaline aqueous solutions 4 6 4 such as SnSe4 4 , Sn2 Se6 , Sn2 Se7 or Sn4Se10 [19]. In contrast to rich molecular species in solutions, limited anionic units have been found in the selenostannate synthesized by flux techniques such as K2MnSn2Se6, K2Ag2SnSe4, K2Ag2Sn2Se6 [4,5,20]. They usually contain the simple building blocks such as [Sn2Se6]4 and SnSe4 units. The building block of Sn3 Se4 8 is very rare in the known selenostannates, never be found in quaternary selenostannates before our work. The syntheses of these compounds and our previous research have shown the advantage of solvothermal method over the flux techniques for synthesis of new quaternary chalcogenides. UV–Vis reflectance spectroscopy was carried out in a range of 190–800 nm, the reflectance data of 1 were converted to the absorption data as described in Ref. [21]. From the absorption data, a band gap of 1.8 eV is estimated, which indicates that 1 is a semiconductor.
Fig. 3. View down a axis of the structure of the compound 2 Grey, Sn; blue, Ag; brown, Se; purple, K. (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
M. Ji et al. / Inorganic Chemistry Communications 10 (2007) 555–557
In conclusion, our preliminary study shows that the glycol plays an important role in the solvothermal reaction. The successful synthesis of A3AgSn3Se8 (A = Rb, K) suggests the possibility of accessing more quaternary selenostannate in the above-mentioned solvothermal system. Acknowledgement We thank the Natural Science Foundation of China for supporting this work (20671015). Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2007. 01.023. References [1] (a) M.R. Dubois, Chem. Rev. 89 (1989) 1; (b) N. Zheng, X. Bu, B. Wang, P. Feng, Science 298 (2002) 2366; (c) M.J. Manos, R.G. Iyer, E. Quarez, J.H. Liao, M.G. Kanatzidis, Angew. Chem. Int. Ed. 44 (2005) 3552; (d) M.K. Brandmayer, R. Clerac, F. Weigend, S. Dehen, Chem. Eur. J. 10 (2004) 5147; (e) J.H. Liao, G.M. Marking, K.F. Hsu, Y. Matsushita, M.D. Ewbank, R. Borwick, P. Cunningham, M.J. Rosker, M.G. Kanatzidis, J. Am. Chem. Soc. 125 (2003) 9484. [2] W.S. Sheldrick, M. Wachhold, Angew. Chem. Int. Ed. Engl. 36 (1997) 206. [3] W.S. Sheldrick, M. Wachhold, Coord. Chem. Rev. 176 (1998) 211. [4] X. Chen, X. Huang, A. Fu, J. Li, L.D. Zhang, H.Y. Guo, Chem. Mater. 12 (2000) 2385. [5] H. Guo, Z. Li, L. Yang, P. Wang, X. Huang, J. Li, Acta. Crystallogr. C57 (2001) 1237. [6] Y.C. Wang, F.J. Disalvo, Chem. Mater. 12 (2000) 1011. [7] S.J. Hwang, R.J. Lyer, P.N. Trikalitis, A.G. Ogden, M.G. Kanatzidis, Inorg. Chem. 43 (2004) 2237. [8] A. Assoud, N. Soheilnia, H. Kleinke, Chem. Mater. 17 (2005) 2255. [9] A. Assoud, N. Soheilnia, H. Kleinke, Chem. Mater. 17 (2005) 4509. [10] N. Ding, D.Y. Choung, M.G. Kanatzidis, Chem. Commun. (2004) 170. [11] M. Wu, W. Su, N. Jasutkar, X. Huang, J. Li, Mater. Research Bull. 40 (2005) 21. [12] C. Zimmermann, M. Melullis, S. Dehnen, Angew. Chem. Int. Ed. 41 (2002) 4269. [13] M. Melullis, C. Zimmermann, C.E. Anson, S. Dehnen, Z. Anorg. Allg. Chem. 629 (2003) 2325.
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[14] E. Ruzin, S. Dehnen, Z. Anorg. Allg. Chem. 632 (2006) 749. [15] J.E. Jerome, P.T. Wood, W.T. Pennington, J.W. Kolis, Inorg. Chem. 33 (1994) 1733. [16] (a) Y. An, M. Ji, M. Baiyin, X. Liu, C. Jia, D. Wang, Inorg. Chem. 42 (2003) 4248; (b) M. Baiyin, Y. An, X. Liu, M. Ji, C. Jia, G. Ning, Inorg. Chem. 43 (2004) 3764; (c) M. Baiyin, L. Ye, Y. An, X. Liu, C. Jia, G. Ning, Bull. Chem. Soc. Jpn. 78 (2005) 1283; (d) Y. An, M. Baiyin, L. Ye, M. Ji, X. Liu, G. Ning, Inorg. Chem. Commun. 8 (2005) 301; (e) H. Duan, Z. Hu, B. Jia, Y. An, Acta Crystallogr. E 62 (2006) 2709. [17] A 0.107 · 0.188 · 0.236 mm3 crystal of 1 was used in diffraction measurements on a Rigaku RAXIS-RAPID diffractometer equipped ˚ ). with graphite monochromatized Mo Ka radiation (k = 0.71073 A Crystal data for 1: Rb3AgSn3Se8 tetragonal, space group P4/nbm, ˚ , b = 8.345(3) A ˚ , c = 13.455(8) A ˚ , M = 1352.03, V = a = 8.345(3) A ˚ 3, Z = 2, qcalc = 4.792 g cm3, F(0 0 0) = 1160, l(Mo Ka) = 937.0(7) A 28.233 mm1, 8249 reflections measured, 589 unique(Rint = 0.0651), which were used in all calculation. The final wR(F2) = 0.119 (all data). Crystal data for 2: K3AgSn3Se8 tetragonal, space group P4/nbm, ˚ , b = 8.096(6) A ˚ , c = 13.384(12) A ˚ , M = 1212.92, a = 8.096(6) A ˚ 3, Z = 2, qcalc = 4.592 g cm3, F(0 0 0) = 1052, l(Mo V = 877.2(12) A Ka) = 22.599 mm1, 7730 reflections measured, 566 unique (Rint = 0.1259), which were used in all calculation. The final wR(F2) = 0.110 (all data). The crystal structure was solved by SHELXS-97 and refined by SHELXL [22]. Absorption correction was performed by a program descried by Higashi [23]. All atom parameters and other crystallographic data for both compounds have also been deposited with the Inorganic Crystal Structure Database of FIZ Karlsruhe as supplementary material with the deposition numbers: 416330 and 416294 for 1 and 2, respectively. These data can be obtained on request at http:// www.fiz-informationsdienste.de/en/DB/icsd; fax: +49 7247 808 666; e-mail: crysdata@fiz-karlsruhe.de. [18] E. Zintl, K. Loosen, Z. Phys. Chem. 174 (1935) 301. [19] B. Krebs, Angew. Chem. Int. Ed. 22 (1983) 113. [20] (a) B. Krebs, J.Z. Uhlen, Z. Anorg. Allg. Chem. 549 (1987) 35; (b) B. Eisenmann, J. Hansa, Z. Kristallogr. 203 (1993) 299; (c) W.S. Sheldrick, B. Schaaf, Z. Anorg. Allg. Chem. 620 (1994) 1041; (d) W.S. Sheldrick, H.G. Braunbek, Z. Naturforsch. B 44 (1989) 851; (e) F. Andreas, B. Roger, Z. Anorg. Allg. Chem. 627 (2001) 411; (f) Z. Chen, R.J. Wang, Acta. Phys. Chim. Sin. 15 (1999) 1070; (g) K.F. Han, Y. Xia, Y.G. Wei, H.Y. Guo, Acta. Chim. Sin. 61 (2003) 724. [21] X. Chen, K.J. Dilks, X. Huang, J. Li, Inorg. Chem. 42 (2003) 3723. [22] (a) G.M. Sheldrick, SHELXS-97: Program for Crystal Structure Determination, University of Gottingen, Germany, 1997; (b) G.M. Sheldrick, SHELXL-97: Program for the Refinement of Crystal Structure, University of Gottingen, Germany, 1997. [23] T. Higashi, Prpgram for Absorption Correction, Rigaku Corporation, Tokyo, Japan, 1995.
Solvothermal syntheses and structures of A3AgSn3Se8 (A = Rb, K) Min Ji a, Menghe Baiyin a, Shouhua Ji b, Yonglin An a
a,*
Department of Chemistry, Dalian University of Technology, Dalian 116024, China Department of Materials, Dalian University of Technology, Dalian116024,China
b
Received 3 December 2006; accepted 24 January 2007 Available online 2 February 2007
Abstract Two new compounds A3AgSn3Se8(A = K, Rb) were synthesized solvothermally and characterized by X-ray single crystal diffraction. These compound are composed of building block [Sn3Se8]4 formed by three edge-sharing SnSe4 tetrahedra, and these building blocks are further connected by tetrahedral coordinated Ag+ to form infinite chains, alkali cations are located between the chains. Their optical properties were also studied. 2007 Elsevier B.V. All rights reserved. Keywords: Solvothermal synthesis; Quaternary selenostannate; Chains structure; Optical properties
In the past decades, syntheses of chalcogenides have received much attention in solid state chemistry and material sciences [1]. Many binary and ternary chalcogenides with interesting structures have been synthesized by various techniques [2,3]. Compared with binary and ternary chalcogenides, the quantity of known quaternary chalcogenides is much less, and quaternary chalcogenides usually were prepared by molten alkali-metal polychalcogenide flux or high-temperature solid state techniques [4–9]. In contrast to chalcogenides prepared hydro(solvo)thermally, most of the high-temperature quaternary phases contain relatively simple building blocks because molecular building blocks such as chains or rings can’t remain to participate in the formation of interesting structures under the high temperature conditions. From the structural point of view, quaternary chalcogenides have more complex structures and interesting properties than binary or ternary ones do due to the complex composition and combination of various structural building blocks. In principle, mild hydro(solvo)thermal method should be an effective route to access new quaternary chacogenides. Under relatively mild conditions, the molecular building blocks can be *
Corresponding author. E-mail address: [email protected] (Y. An).
1387-7003/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2007.01.023
assembled to a fascinating variety of quaternary chacolgenides. However solvothermal synthesis has produced a limited number of quaternary chalcogenides up to now [10– 14]. To some extent, this situation results from deficient research on mineralizers for the synthesis. In spite of some synthetic strategies such as usage of supercritical conditions have been developed [15], lack of effective mineralizers retards successful hydro(solvo)thermal synthesis of quaternary chacogenides. Recently, our exploratory research has demonstrated that HSCH2CH(SH)CH2OH is a very good mineralizer for solvothermal synthesis of various sulfides [16]. With an aim of searching for an effective mineralizer, we carried out the investigation on solvothermal synthesis of quaternary selenostannate [16]. In this publication, we report a solvothermal synthesis of two novel quaternary selenostannate in the presence of glycol. The synthesis of Rb3AgSn3Se8 (1) was as follows: 0.010 g of powder Ag , 0.060 g of Sn, 0.060 g of powder Se, and 0.120 g of Rb2CO3 were put into a Pyrex glass tube, to which 0.6 mL of pyridine/glycol = 2:1 was added. The glass tube was sealed with a 10% filling, placed into a Teflon-lined stainless steel autoclave, and heated at 180 C for 7 days. The products were washed with ethanol and water, respectively, pure red crystals were obtained with a 70% yield based on silver. A composition analysis
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M. Ji et al. / Inorganic Chemistry Communications 10 (2007) 555–557
by an energy-dispersive spectrum collected by a scanning electron microscope indicated the presence of Se, Rb, Ag, and Sn in a 54.20:17.63:7.21:20.96 molar ratio, which is consistent with that expected from the following crystal structure determination. By the above method, a pure compound K3AgSn3Se8 (2) was also obtained. Our research showed that glycol is essential for the synthesis, the effect of glycol may result from the formation of some selenoglycol , which can play a role of the mineralizer. Crystal structure analysis showed that compounds 1 and 2 are isostructural, consisted of linear building block Sn3 Se4 8 , in which three tetrahedral SnSe4 share their edges [17]. These building blocks Sn3 Se4 8 are further connected by Ag+ ions to form infinite single chains as shown in Fig. 1. Each chain has a C2 rotational symmetry along the c direction, and the adjacent chain has different tetrahedral orientation as seen in Fig. 2. The rotational symmetry of the chains result in each tetrahedral AgSe4 and the middle SnS4 of Sn3 Se4 have only one kind of bond 8 lengths, and two side SnSe4 tetrahedra are identical, and with two kind of bond lengths, and terminal Sn–Se of Sn3 Se4 is longer than bridging Sn–Se. In compound 1, 8 the middle SnSe4 of Sn3 Se4 has the bond length of 8 ˚ for its four Sn–Se bonds and bond angles Se–Sn– 2.515 A
Fig. 1. A single chain ½AgSn3 Se3 3 1 of compound 2 showing the C2 symmetry along c direction and linkage between the building unit [Sn3Se8]4 and Ag+. Grey, Sn; blue, Ag; brown, Se. (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. The adjacent chains with different tetrahedral orientations in the compound 2. Grey tetrahedra, SnSe4; blue tetraheda, AgSe4. (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
Se between 97.39 and 115.83, the side tetrahedral SnSe4 are distorted slightly with the bond length of Sn–Se ˚ and 2.620 A ˚ , respectively, and bond angles Se– 2.473 A Sn–Se in the range of 92.30–112.92. The tetrahedral AgSe4 ˚ , and bond angles Se–Ag– have the bond length of 2.794 A Se 95.11–117.09. In compound 2, the middle tetrahedral ˚ and bond angles SnSe4 has the bond length of 2.521 A Se–Sn–Se between 97.41 and 115.82. For the side tetrahe˚ and 2.616 A ˚, dral SnSe4, the bond lengths are 2.478 A respectively, and the bond angles in the range of 92.74– 112.47. The tetrahedral AgSe4 have the bond length of ˚ and bond angles 96.23–116.47. From above com2.771 A parison, it can be seen that alkali cations located between anionic chains have a little effect on the bond lengths and angles of tetrahedra in the chain, indicating the covalent nature of the bonding in the chain (see Fig. 3). The linkage of tetrahedral Sn and Ag in compounds 1 and 2 is the same as that in the structure of SiS2, in which tetrahedral SiS4 shares their edges to form a single chain [18]. This kind of linkage also implies the strong covalent characteristics of these compounds. Krebs and co-workers showed that various tetrahedral selenostannate anions exist in alkaline aqueous solutions 4 6 4 such as SnSe4 4 , Sn2 Se6 , Sn2 Se7 or Sn4Se10 [19]. In contrast to rich molecular species in solutions, limited anionic units have been found in the selenostannate synthesized by flux techniques such as K2MnSn2Se6, K2Ag2SnSe4, K2Ag2Sn2Se6 [4,5,20]. They usually contain the simple building blocks such as [Sn2Se6]4 and SnSe4 units. The building block of Sn3 Se4 8 is very rare in the known selenostannates, never be found in quaternary selenostannates before our work. The syntheses of these compounds and our previous research have shown the advantage of solvothermal method over the flux techniques for synthesis of new quaternary chalcogenides. UV–Vis reflectance spectroscopy was carried out in a range of 190–800 nm, the reflectance data of 1 were converted to the absorption data as described in Ref. [21]. From the absorption data, a band gap of 1.8 eV is estimated, which indicates that 1 is a semiconductor.
Fig. 3. View down a axis of the structure of the compound 2 Grey, Sn; blue, Ag; brown, Se; purple, K. (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
M. Ji et al. / Inorganic Chemistry Communications 10 (2007) 555–557
In conclusion, our preliminary study shows that the glycol plays an important role in the solvothermal reaction. The successful synthesis of A3AgSn3Se8 (A = Rb, K) suggests the possibility of accessing more quaternary selenostannate in the above-mentioned solvothermal system. Acknowledgement We thank the Natural Science Foundation of China for supporting this work (20671015). Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2007. 01.023. References [1] (a) M.R. Dubois, Chem. Rev. 89 (1989) 1; (b) N. Zheng, X. Bu, B. Wang, P. Feng, Science 298 (2002) 2366; (c) M.J. Manos, R.G. Iyer, E. Quarez, J.H. Liao, M.G. Kanatzidis, Angew. Chem. Int. Ed. 44 (2005) 3552; (d) M.K. Brandmayer, R. Clerac, F. Weigend, S. Dehen, Chem. Eur. J. 10 (2004) 5147; (e) J.H. Liao, G.M. Marking, K.F. Hsu, Y. Matsushita, M.D. Ewbank, R. Borwick, P. Cunningham, M.J. Rosker, M.G. Kanatzidis, J. Am. Chem. Soc. 125 (2003) 9484. [2] W.S. Sheldrick, M. Wachhold, Angew. Chem. Int. Ed. Engl. 36 (1997) 206. [3] W.S. Sheldrick, M. Wachhold, Coord. Chem. Rev. 176 (1998) 211. [4] X. Chen, X. Huang, A. Fu, J. Li, L.D. Zhang, H.Y. Guo, Chem. Mater. 12 (2000) 2385. [5] H. Guo, Z. Li, L. Yang, P. Wang, X. Huang, J. Li, Acta. Crystallogr. C57 (2001) 1237. [6] Y.C. Wang, F.J. Disalvo, Chem. Mater. 12 (2000) 1011. [7] S.J. Hwang, R.J. Lyer, P.N. Trikalitis, A.G. Ogden, M.G. Kanatzidis, Inorg. Chem. 43 (2004) 2237. [8] A. Assoud, N. Soheilnia, H. Kleinke, Chem. Mater. 17 (2005) 2255. [9] A. Assoud, N. Soheilnia, H. Kleinke, Chem. Mater. 17 (2005) 4509. [10] N. Ding, D.Y. Choung, M.G. Kanatzidis, Chem. Commun. (2004) 170. [11] M. Wu, W. Su, N. Jasutkar, X. Huang, J. Li, Mater. Research Bull. 40 (2005) 21. [12] C. Zimmermann, M. Melullis, S. Dehnen, Angew. Chem. Int. Ed. 41 (2002) 4269. [13] M. Melullis, C. Zimmermann, C.E. Anson, S. Dehnen, Z. Anorg. Allg. Chem. 629 (2003) 2325.
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