本論文主要是利用助熔劑長晶法合成兩個系列的化合物，第一系列是錫矽酸鹽化合物其中有包含鹽類 (salt-inclusion compound) [Na3F][SnSi3O9] (1) 與無機陽離子 Cs2SnSi6O15 (2)、Cs2SnSi3O9 (3) 這兩種類型的錫矽酸鹽化合物，第二系列是錫鍺酸鹽化合物 Na4Sn2Ge5O16 (4)。藉由 X 光單晶繞射法決定出結構與化學式，並利用固態核磁共振的方法探討特定原子核的周遭環境與 X 光單晶繞射法所得的結果相互佐證。
化合物 1 是一個嶄新的結構，從過去的文獻中從未報導過金屬矽酸鹽同時包含 Na+ 離子與 F- 離子同時填充於孔洞中形成類似 anti-Al2Cl6 的結構，而化合物 2 、化合物 3 皆是三維的結構，矽酸鹽的部份分別形成二維的矽酸鹽骨架及一維直鏈狀的矽酸鹽，化合物 4 是一個新穎的錫鍺酸鹽化合物，鍺氧四面體是以共角的方式相互連接，形成 [Ge5O16] 的五重體鏈 (fivefold germanate tetrahedra)，以 SnO6 八面體連接這五重體鏈，形成具有兩種不同形式的六員環，而這兩種六員環又以相互交叉 (intersection tunnels) 的形式存在，並將此化合物與文獻中一些類似分子式的化合物做一系列的比較。

Four new Metal silicates and Metal germanates, [Na3F][SnSi3O9](1)、Cs2SnSi6O15(2)、Cs2SnSi3O9 (3)、Na4Sn2Ge5O16 (4) have been synthesized using a flux-growth method and characterized by single-crystal X-ray diffraction. The structure of 1 consists of 6-membered silicate rings linked via corner-sharing by SnIVO6 octahedra to form a 3-D framework that delimits two types of channels. The F atoms and Na atoms are located in the structural channels and form a dimer with the anti-Al2Cl6(g) structure. This stannosilicate adopts a new structure and is the first metal silicate that contains both Na+ and F- ions in the channels. The 19F and 29Si MAS NMR and 23Na MQMAS NMR spectra are consistent with the crystallographic results. Crystal data: [Na3F][SnSi3O9], monoclinic, space group C2/m (No. 12), a = 10.539(1) Å, b = 13.953(2) Å, c = 6.5171(7) Å, ? = 111.576(2)º, V = 891.2(3) Å3, and Z = 4. The structure of 2 can be expressed in terms of Si6O156- silicate sheets by isolated SnO6 octahedra. The structure of 3 consists of unbranched infinite chain, periodically repeating unit every six tetrahedral. These chains are linked by SnIVO6 octahedra. The structure of 4 is based on [Ge5O16] ( fivefold germanate tetrahedra) that are connected by SnIVO6 octahedra to form 3-D framework. The structure consists of two types of six-membered rings and forms the intersection tunnels.

1. Davis, M. E. Nature 2002, 417, 813-821
2. Cheetham, A. K.; Férey, G.; Loiseau, T. Angew. Chem. Int. Ed. 1999,
38, 3268.
3. Feryhardt, C. C.; Tsapatsis, M.; Lobo, R. F.; Balkus, K. J.; Davis, M.
E. Nature 1996, 381, 295.
4. Wagner, P.; Yoshikawa, M.; Tsuji, K.; Tsapatsis, M.; Davis, M. E.
Chem. Commun. 1997, 2179.
5. Burton, A.; Elomari, S.; Chen, C. Y.; Medrud, R. C.; Chan, I. Y.; Bull,
L. M.; Kibby, C.; Harris, T. V.; Zones, S. I.; Vittoratos, E. S. Chem.
Eur. Journal 2003, 9, 5737.
6. Vaughan, D. E. W.; Strohmaier, K. G. J. Am. Chem. Soc. 2003, 125,
16035.
7. Harbuzaru, B.; Paillaud, J. L.; Patarin, J.; Bats, N. Science 2004, 304,
990.
8. Cheetham, T.; Fjellag, H.; Gier, T. E.; Kongshaug, K. O.; Lillerud, K.
P.; Stucky, G. T. Stud. Surf. Sci. Catal. 2001, 135, 788.
9. Zhou Y.; Zhu H.; Chen Z.; Chen M.; Xu, Y.; Zhang H.; Zhao D.
Angew. Chem. Int. Ed. 2001, 40, 2166.
10. Plévert, J.; Gentz, T. M.; Laine A.; Li, H.; Young, V. G.; Yaghi, O. M.;
O’Keefe M. J. Am. Chem. Soc. 2001, 123, 12706.
11. Li, H.; Eddaoudi, M.; Richardson, M.; Richardson, D. A.; Yaghi, O.
M. J. Am. Chem. Soc. 1998, 120, 8567.
12. Bu, X.; Feng, P.; Gier, T. E.; Zhao, D.; Stucky, G. D. J. Am. Chem.
Soc. 1998, 120, 13389.
13.(a) Wirnsberger, G.; Stucky, G. D. Chem. Mater. 2000, 12, 2525.
(b) Wada, Y. et al. J. Am. Chem. Soc. 2000, 122, 8583.
14. Crabtree, R. H. Nature 2000, 408, 415.
15. (a) Hung, L.-I.; Wang, S.-L.; Kao, H.-M.; Lii, K.-H. Inorg. Chem.
2003, 42, 4057.(b) Hung, L.-I.; Wang, S.-L.; Szu, S.-P.; Hsieh,
C.-Y.; Kao, H.-M.; Lii,K.-H. Chem. Mater. 2004, 16, 1660.(c)
Hung, L.-I.; Wang, S.-L.; Chen, C.-Y.;Chang, B.-C.; Lii, K.-H. Inorg.
Chem. 2005, 44, 2992.
16. (a) Wang, X.; Liu, L.; Zhang, G.; Jacobson, A. J. Chem. Commun.
2001, 2472. (b) Wang, X.; Liu, L.; Jacobson, A. J. Angew. Chem. Int.
Ed. 2001, 40, 2174. (c) Brandao, P.; Philippou, A.; Hanif, N.; Claro,
P. R.; Ferreira, A.; Anderson, M. W.; Rocha, J. Chem. Mater. 2002,
14, 1053. (d) Wang, X.; Liu, L.; Jacobson, A. J. J. Am. Chem. Soc.
2002, 124, 7812. (e) Haung, J.; Wang, X.; Liu, L.; Jacobson, A. J.
Solid State Sciences 2002, 4, 1193. (f) Li, C.-Y.; Hsieh,C.-Y.; Lin,
H.-M.; Kao, H.-M.; Lii, K.-H. Inorg. Chem. 2002, 41, 4206.
(g)Tripathi, A.; Hughbanks, T.; Clearfield, A. J. Am. Chem. Soc.
2003, 125,10528. (h) Brandao, P.; Valente, A.; Philippou, A.;
Ferreira, A.; Anderson, M.W. Rocha, J. Eur. J. Inorg. Chem. 2003,
1175.
17. (a)Ananias, D.; Ferreira, A.; Rocha, J.; Ferreira, P.; Rainho, J. P.;
Morais, C.; Carlos, L. D. J. Am. Chem. Soc. 2001, 123, 5735. (b)
Ferreira, A.; Ananias, D.; Carlos, L. D.; Morais, C. M.; Rocha, J.
J.Am.Chem. Soc. 2003, 125, 14573. (c) Rocha, J.; Ferreira, P.; Carlos,
L. D.; Ferreira, A. Angew. Chem. Int. Ed. 2000, 39, 3276. (c) Jeong,
H.-K.; Chandrasekaran, A.; Tsapatsis, M. Chem. Commun.
2002, 2398. (d) Haile, S. M.; Wuensch, B. J. Acta Crystallogr. 2000,
B56, 335. (e) Haile, S. M.; Wuensch, B. J. Acta Crystallogr. 2000,
B56, 349.
18. (a) Brown, I. D.; Altermart, D. Acta Cryst. 1985, 24, 1026.
(b) 李光華, 化學 , 1994, 52, 405.
19. Ladd, M. F.; Palmer, R. A. Structure Determination by X-ray
Crystallography, Plenum, New York, 1994.
20. SAINT, Program for Data Extraction and Reduction, Siemens
Analytical X-ray Instruments Inc., Madison, USA, 1996.
21. Sheldrick, G. M. SHELXTL Programs, version 5.1; Bruker AXS
GmbH: Karlsruhe, Germany, 1998.
22. I. D. Brown, Altermatt, D. Acta Cryst. 1985, B41, 244.
23. 高憲明, 化學 , 2004, 62 , 255.
24. Frydman, L.; Harwood, J. S. J. Am. Chem. Soc. 1995, 117, 5367.
25. (a) Huang, Q.; Ulutagay, M.; Michener, P. A.; Hwu, S.-J. J. Am. Chem. Soc. 1999, 121, 10323. (b) Huang, Q.; Hwu, S.-J.; Mo, X. Angew. Chem. Int. Ed. 2001, 40, 1690. (c) Hwu, S.-J.; Ulutagay-Kartin, M.; Clayhold, J. A.; Mackay, R.; Wardojo, T. A.; O’Connor, C. J.; Krawiec, M. J. Am. Chem. Soc. 2002, 124, 12404. (d) Huang, Q.; Hwu, S.-J. Inorg. Chem. 2003, 42, 655. (e) Mo, X.; Hwu, S.-J. Inorg. Chem. 2003, 42, 3978. (f) Mo, X.; Ferguson, E.; Hwu, S.-J. Inorg. Chem. 2005, 44, 3121.
26. (a) Vaidhyanathan, R.; Neeraj, S.; Prasad, P. A.; Natarajan, S.; Rao, C.
N. R. Angew. Chem. Int. Ed. 2000, 39, 3470. (b) Vaidhyanathan, R.; Natarajan, S.; Rao, C. N. R. J. Solid State Chem. 2002, 167, 274.(c) Vaidhyanathan, R.; Natarajan, S.; Rao, C. N. R. Mater. Res. Bull. 2003, 38, 477.
27. Schmidt, A.; Glaum, R. Inorg. Chem. 1997, 36, 4883
28. Liebau, F. Structural Chemistry of Silicates. Springer, Berlin, 1985.
29. Brown, I. D.; Altermatt, D. Acta Crystallogr. 1985, B41, 244.
30. MacKenzie, K. J. D.; Smith, M. E. Multinuclear Solid-State NMR of Inorganic Materials, Pergamon, 2002.
31. Rocha, J.; Anderson, M. W. Eur. J. Inorg. Chem. 2000, 801.
32. Rocha, J.; Brandao, P; Lin, Z.; Anderson, M. W.; Alfredsson, V.;
Terasaki, O. Angew. Chem. Int. Ed. 1997, 36, 100.
33. (a) Rocha, J.; Ferreira, P.; Carlos, L. D.; Ferreira, A. Angew.
Chem. Int. Ed. 2000, 39, 3276. (b) Jeong, H.-K.; Chandrasekaran, A.;
Tsapatsis, M. Chem.Commun. 2002, 2398.
34. Lin, Z.; Rocha, J.; Valente, A. Chem. Commun. 1999, 24, 2489.
35. Poojary, D. M.; Bortun, A. I.; Bortun, L. N.; Clearfield, A. Inorg.
Chem. 1997, 36, 3072.
36. Lin, Z.; Ferreira, A.; Rocha, J. J. Solid State Chem. 2003, 175, 258.
37. Ferreira, A.; Lin, Z.; Rocha, J.; Morais, C. M.; Lopes, M.; Fernandez, C. Inorg. Chem. 2001, 40, 3330.
38. Ferreira, A.; Lin, Z.; Soares, M. R.; Rocha, J. Inorg. Chim. Acta.
2003, 356, 19.
39. Lo, F. -R.; Lii, K. -H. J. Solid State Chem. 2005, 178, 1017.
40. Jolicart, G.; Leblanc M. Eur. J. Solid State Inorg. Chem. 1999, 33,
647.
41. (a) O’Keeffe, M.; Yaghi, O. M. Chem. Eur. J. 1999, 5, 2796. (b)
Cascales, C.; Gutiérrez-Puebla, E.; Iglesias, M.; Monge, M. A.;
Ruiz-Valero, C. Angew. Chem., Int. Ed. Engl. 1999, 38, 2436.
(c) Cascales, C.; Gutiérrez-Puebla, E.; Iglesias, M.; Monge, M. A.;
Ruiz-Valero, C.; Snejko, N. Chem. Commun. 2000, 2145. (d)
Conradsson, T.; Dadachov, M. S.; Zou, X. D. Microporous
Mesoporous Mater. 2000, 41, 183. (e) Dadachov, M. S.; Sun, K.;
Conradsson, T.; Zou, X. Angew. Chem., Int. Ed. 2000, 39, 3674.
(f) Li, H.; Eddaoudi, M.; Plévert, J.; O’Keeffe, M.; Yaghi, O. M. J.
Am. Chem. Soc. 2000, 122, 12409.
42. Plévert, J.; Sanchez-Smith, R. S.; Gentz, T. M.; Li, H.; Groy, T. L.;
Yaghi, O.M.; O’Keeffe, M. Inorg. Chem. 2003, 42, 5954.
43. Brese, N. E.; O’Keefe, M. Acta Crystallogr. 1991, B47, 192.
44. Safronov, A. N.; Nevskii, N. N.; Ilyukhin, V. V.; Belov, N. V. Sov.
Phys. Dokl. 1982, 27, 991.
45. Schannon, R. D. Acta Crystallogr. 1976, A32, 751.