臺灣博碩士論文加值系統

合成Free base 2-NC3H5NCTPPH (1)再與金屬試劑CoCl2 • 6H2O及ZnCl2反應得到Co(2-NC3H5-21-p-CH2C6H4CH3NCTPP)Cl (2)、Co(2-NC3H5-21-m-CH2C6H4CH3NCTPP)Cl (3)、Co(2-NC3H5-21-o-CH2C6H4CH3NCTPP)Cl (4) 、Co(2-NC3H5-21-CH2C6H5NCTPP)Cl (5) 和Zn(2-NC3H5-21-H-NCTPP)Cl (6)。
藉由X-ray單晶繞射得其結構，核磁共振光譜儀變溫實驗得Zn(2-NC3H5-21-H-NCTPP)Cl之o-H(22A, 26A)之交換活化能。並以超導量子干涉儀測定磁性並得鈷錯合物之軸向零場開裂(D)值，探討其值與晶體結構之關聯。

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(II) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2•6H2O in toluene (or o-xylene, m-xylene, p-xylene), and the structures were revealed by single-crystal X-ray analysis.The axial zero-field splitting parameter D was found to vary from 46.9 cm-1 in 2 to 42.0 cm-1 in 3, 34.7 cm-1 in 4 and 35.6 cm-1 in 5 by paramagnetic susceptibility measurements. The magnitude of D can be related to the coordination sphere at the cobalt sites.

摘要 i
Abstract ii
目錄 iii
表目錄 vi
圖目錄 vii
第一章 緒論 1
一、 引言 2
二、 紫質的簡介 2
三、 N-confused porphyrin之合成 3
四、 N-confused porphyrin之N-烷基化修飾 4
五、 實驗室研究方向 4
第二章 實驗方法與藥品 6
一、 N-confused tetraphenylporphyrin ( NCTPP ) 之合成 7
二、 2-NC3H5NCTPPH之合成 8
三、 Co(2-NC3H5-21-p-CH2C6H4CH3NCTPP)Cl之合成 9
四、 Co(2-NC3H5-21-m-CH2C6H4CH3NCTPP)Cl之合成 10
五、 Co(2-NC3H5-21-o-CH2C6H4CH3NCTPP)Cl之合成 11
六、 Co(2-NC3H5-21-CH2C6H5NCTPP)Cl之合成 12
七、 Zn(2-NC3H5-21-H-NCTPP)Cl之合成 13
八、 實驗用藥品 15
九、 數據測量方法 17
第三章 結果與討論 20
一、 X-ray單晶數據 21
I. 2-NC3H5NCTPPH之數據 21
II. Co(2-NC3H5-21-p-CH2C6H4CH3NCTPP)Cl之數據 23
III. Co(2-NC3H5-21-m-CH2C6H4CH3NCTPP)Cl之數據 25
IV. Co(2-NC3H5-21-o-CH2C6H4CH3NCTPP)Cl之數據 27
V. Co(2-NC3H5-21-CH2C6H5NCTPP)Cl之數據 29
VI. Zn(2-NC3H5-21-H-NCTPP)Cl之數據 31
二、 NMR光譜數據 38
I. 2-NC3H5NCTPPH之數據 38
II. Zn(2-NC3H5-21-H-NCTPP)Cl之數據 (293 K) 45
III. Zn(2-NC3H5-21-H-NCTPP)Cl之數據 (變溫) 50
三、 SQUID數據 55
四、 UV-Vis-NIR與EPR數據 61
第四章 總結 63
第五章 附錄 67
一、 晶體check CIF 68
二、 質譜 74
三、 UV-Vis光譜及NIR光譜 79
四、 EPR光譜 84
五、 元素分析 86

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