臺灣博碩士論文加值系統

本研究以助熔長晶法，合成出兩種不同結構化合物。分別為化合物1、化合物2。
化合物1其晶系為Orthorhombic Pnma。此結構利用CuSe3、MSe4 (M = Cu、In)形成3D立體結構骨架，並且InSe4形成四面體以共用點串接沿b軸延伸和陽離子Ba2+填充在孔道中。化合物1因為部分原子位置有Cu和In的錯排(disorder)，造成解出分子式不平衡。因此，以佔有率及價數平衡原則解出分子式，並以分子式嘗試純相合成。
化合物2，其晶系為Monoclinic P21/m。此結構利用InTe3、MTe4、MTe5 (M = Ag或In)形成3D立體結構骨架。在孔洞中，MTe4 四面體以共用點沿b軸串接和陽離子Ba2+一起填充在孔道中。化合物2因為Ag、In無法藉由X-ray分辨電子密度。由B. V. S. (Bond valence sum)輔證，部分原子位置有Ag和In的混填，由程式指令精算有問題位置皆為發散。因此，以佔有率及價數平衡原則解出分子式，並以分子式嘗試更好單晶合成條件。

Two new compounds, 1 and 2, have been synthesized through solid state reactions with KBr flux.

Compound 1 crystallizes in the orthorhombic Pnma, which adopts a new three-dimensional framework structure. The framework in 1 is composed of two distinct infinite chain with Ba2+ cations distributed within the tunnels.The first chain is constructed by CuSe3 triangular plane and MSe4 (M = Cu, In) tetrahedral.The second chain is constructed by InSe4 tetrahedral.

Compound 2 crystallizes in the monoclinic P21/m, which possesses a new three-dimensional framework structure. The framework in 2 is composed of InTe3 triangular plane, MTe4 tetrahedral, and MTe5 (M = Ag or In) polyhedra with Ba2+ cations distributed within the tunnels.

摘要 1
Abstract 2
致謝 3
目錄 4
圖目錄 6
表目錄 8
第一章 緒論 10
第二章 13
金屬硫族化合物之合成與鑑定 13
2.1 合成 13
2.2 單晶X光繞射分析 15
2.3 能量散佈光譜儀 22
2.4 粉末X光繞射分析 22
2.5 微差熱分析 23
2.6 紫外-可見-近紅外光光譜儀 24
第三章 結果與討論 25
3.1 結構描述 25
3.1.1 化合物1結構描述 26
3.1.2 化合物2結構描述 35
3.2 物理性質 43
3.2.1 化合物1性質描述 43
第四章 結論 49
第五章 參考文獻 50
第六章 附錄 52

[1]Chung, D. Y., Hogan,T., and Brazis, P. Science 2000, 287, 1024.
[2]Chung, D. Y., Choi, K. S, and Lykourgos Iordanidis Chem.Meter. 1997, 9, 3060.
[3]Tritt, T. M. Science 1999, 283, 804.
[4]Cui, Y., Assoud, A., and Kleinke, H. Inorg. Chem. 2009, 48, 5313.
[5]Finlayson, N., Banyai, W. C., and Seaton, C. T. J. Opt. Soc. Am. 1989, 6B, 675.
[6]Kim, Y., Seo, I. S., Martin, S. W., Baek, J., Halasyamani, P. S., Arumugam, N., and Steinfink, H. Chem. Mater. 2008, 20, 6048.
[7]Adam, A. Mater. Res. Bull. 2007, 42, 1986.
[8]Nada, Y., Ohba, S., Sato, S., Saito, Y. Acta Cryst. 1983, B39, 312.
[9]S. C. Abrahams, J. L. Bernstein, J. Chem. Phy. 1973, 59, 1625.
[10]S. C. Abrahams; J. L. Bernstein, J. Chem. Phy. 1974, 61, 1140.
[11]Chung, D. Y., Choi, K. S., Iordanidis, L., Schindler, J. L., Brazis, P. W., Kannewurf, C. R., Chen, B., Hu, S., Uher, C., and Kanatzidis, M. G. Chem. Mater. 1997, 9, 3060.
[12]Mrotzek, A., Chung, D.Y., Hogan, T., and Kanatzidis, M. G. J. Mater. Chem. 2000, 10, 1667.
[13]Androulakis, J., Hsu, K. F., Kong, H., Uher, C., D’Angelo, J. J., Downey, A., Hogan, T., and Kanatzidis, M. G. Adv. Mater. 2006, 18, 1170.
[14]Derakhshan S., Assoud A., Taylor N. J., and Kleinke H. Intermetallics 2006, 14, 198.
[15]Chung D. Y., Hogan T. P., Rocci-Lane M., Brazis P., Ireland J. R., Kannewurf C. R., Bastea M., Uher C., and Kanatzidis M. G. J. Am. Chem. Soc. 2004, 126, 6414.
[16]Slack G. A., in CRC Handbook of Thermoelectrics, ed. D. M. Rowe,CRC Press, Boca Raton, 1995.
[17]Michael A. McGuire, Andrew F. May, David J. Singh, Mao-Hua Du, Gerald E. Jellison, M.A. McGuire. Solid State Chem. 2011, 184, 2744–2750.
[18]Wang, Y. C., DiSalvo, and F. J. J. Solid State Chem. 2001, 156, 44.
[19]Cui, Y., Assoud, A., Xu, J., and Kleinke,H. Inorg. Chem. 2007, 46, 1215.
[20]Assoud, A., Cui, Y., Thomas, S., Sutherland, B., and Kleinke, H. J. Solid State Chem. 2008, 181, 2024.
[21]Assoud, A., Thomas, S., Sutherland, B., Zhang, H., Tritt, T. M., and Kleinke, H. Chem. Mater. 2006, 18, 3866.
[22]Patschke, R., Zhang, X., Singh, D., Schindler, J., Kannewurf, C. R., Lowhorn, N., Tritt, T., Nolas, G. S., and Kanatzidis, M. G. Chem. Mater. 2001, 13, 613.
[23]Tampier,M. and Johrendt,D. Z. Anorg. Allg. Chem. 2001, 627, 312.
[24]Sheldrick, G. M., SHELXL-97, University of Göttingen, Germany,
1997.
[25]Spek, L. Acta Cryst. 1990, A46, C34.
[26]Yanjie Cui, Abdeljalil Assoud, Holger Kleinke, Inorg. Chem. 2009, 48, 5313–5319.
[27]Tonci, B. Z., Konstantin, M., Karen, F., Emil, M. Acta Cryst. 2005, B61,239.
[28]Kocman, V., Nuffield, E. W. Acta Cryst. 1973, B29,2528.
[29]Pfitzner, A., Zimmerer, S. Angew. Chem. Int. Ed. Engl. 1997, 36, 982.
[30]Pawley, G. S. J. Appl. Crystallogr. 1981, 14, 357