臺灣博碩士論文加值系統

本論文是利用"對-溴甲基異丙基苯"做為烷化試劑來修飾N-confused porphyrin(NCP)，生成2-NCH2-p-C6H4-isoC3H7NCTPPH (2)，接著將(2)分別與鎳(Nickel)、鈀(Palladium)、鉑(Platinum)、鈷(Cobalt)之金屬試劑反應，得到以下四種金屬錯合物：
Ni(2-NCH2-p-C6H4-isoC3H7NCTPP) (3)、Pd(2-NCH2-p-C6H4-isoC3H7NCTPP) (4)、Pt(2-NCH2-p-C6H4-isoC3H7NCTPP) (5)、Co(2-NCH2-p-C6H4-isoC3H7-21-CH2-p-C6H4CH3-NCTPP)Cl (6)。
藉由X-ray單晶繞射儀、核磁共振光譜儀、電子順磁共振光譜儀、超導量子干涉儀、紫外光-可見光光譜儀、紫外光-可見光-近紅外光光譜儀、質譜儀、元素分析等儀器，來鑑定並研究金屬錯合物之物理化學性質。
金屬錯合物Ni (3)、Pd (4)、Pt (5)的幾何構型為扭曲方形平面，Co (6)為扭曲四面體。Co (6)為高自旋單核順磁性化合物(S = 3/2)，基態項符為4A2(F)，將其溶於甲苯，4 K，以X-band，垂直模式之EPR光譜，測得geff = [gx(eff), gy(eff), gz(eff)] = [1.92, 3.73, 6.18]。利用SQUID數據與EPR光譜求得零場開裂常數D = 29.35 cm-1，E = 6.46 cm-1。

We use isopropyl benzyl bromide as alkylation reagent to react with N-confused porphyrin (NCP) to afford 2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrin [2-NCH2-p-C6H4-isoC3H7NCTPPH; 2]. Then we use Ni(OAc)2∙4H2O, PdCl2, PtCl2 and CoCl2∙6H2O as metal source to react with (2) seperately to get four NCP metal complexes: (2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′,N′′) nickel(II) [Ni(2-NCH2-p-C6H4-isoC3H7NCTPP); 3], (2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′,N′′) palladium(II) [Pd(2-NCH2-p-C6H4-isoC3H7NCTPP); 4], (2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′,N′′) platinum(II) [Pt(2-NCH2-p-C6H4-isoC3H7NCTPP); 5], and chloro(2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21- p-xylyl-21-carbaporphyrinato-N,N′,N′′) cobalt(II) [Co(2-NCH2-p-C6H4-isoC3H7-21-CH2-p-C6H4CH3-NCTPP)Cl; 6].
Appling X-ray single-crystal diffractometer, Nuclear magnetic resonance spectrometer, Electron paramagnetic resonance spectrometer, Superconducting quantum interference device magnetometer, UV-visible spectrophotometer, UV-visible-NIR spectrophotometer, Elemental analyzer, Mass spectrometer to characterize and study the crystal structures of NCP metal complexes and their physical chemistry property.
The crystal structures of free base (2), diamagnetic complexes (3), (4), (5) and paramagnetic complex (6) were determined. The coordination sphere around Ni2+, Pd2+ and Pt2+ ions in 3 - 5 are distorted square planar (DSP), whereas for Co2+ in 6, it is distorted tetrahedron (DT). The effective g value, geff = [gx(eff), gy(eff), gz(eff)] = [1.92, 3.73, 6.18] measured from the perpendicular polarization of X-band EPR spectra for 6 in toluene at 4 K is consistent with a 4A2(F) ground term for a high spin mononuclear cobalt (II) (S = 3/2) in 6. The magnitudes of axial (D) and rhombic (E) zero-field splitting (ZFS) for the mononuclear Co(II) in 6 were determined approximately as 29.35 cm-1 and 6.46 cm-1.

摘要 i
Abstract ii
目錄 iv
表目錄 vii
圖目錄 viii
第一章 序論 1
一、前言 2
二、氮碳異位紫質: N-confused porphyrin 3
(1) N-confused porphyrin (NCP)的發現與合成 3
(2) N-confused porphyrin (NCP)的性質與互變異構物形態 6
(3) N-confused porphyrin(NCP)的2-N位置烷化反應 8
三、實驗室研究方向 9
第二章 實驗部分 11
一、Preparation of N-confused tetraphenylporphyrin (1) 12
二、Preparation of 2-NCH2-p-C6H4-isoC3H7NCTPPH (2) 14
三、Preparation of Ni(2-NCH2-p-C6H4-isoC3H7NCTPP) (3) 16
四、Preparation of Pd(2-NCH2-p-C6H4-isoC3H7NCTPP) (4) 17
五、Preparation of Pt(2-NCH2-p-C6H4-isoC3H7NCTPP) (5) 18
六、Preparation of Co(2-NCH2-p-C6H4-isoC3H7-
21-CH2-p-C6H4CH3-NCTPP)Cl (6) 19
七、實驗藥品與溶劑 21
八、儀器與測定方式 23
第三章 結果與討論 26
X-ray單晶結構分析；1H NMR光譜數據；13C NMR光譜數據；
MS、EA、UV-vis數據；Uv-vis-NIR；EPR；SQUID
第一節 2-N substituted N-confused porphyrin: free base 27
2-NCH2-p-C6H4-isoC3H7NCTPPH (2) 28
第二節 Diamagnetic N-confused porphyrin complexes 35
一、Ni(2-NCH2-p-C6H4-isoC3H7NCTPP) (3) 36
二、Pd(2-NCH2-p-C6H4-isoC3H7NCTPP) (4) 43
三、Pt(2-NCH2-p-C6H4-isoC3H7NCTPP) (5) 50
第三節 Paramagnetic N-confused porphyrin complex 58
Co(2-NCH2-p-C6H4-isoC3H7-21-CH2-p-C6H4CH3-NCTPP)Cl (6) 59
第四節 討論部分 71
一、Iminium ion pairs [N(4)+=CH(19)(Ar)]之探討 72
二、195Pt之NMR光譜研究 80
三、高自旋單核Cobalt(II) (S = 3/2)錯合物之性質探討 84
(1)SQUID數據分析 86
(2)UV-vis-NIR光譜探討 88
(3)EPR光譜探討 90
(4)Van Vleck’s equation推導for Co(II)
(d7，Td，S = 3/2) 92
第四章 結論 94
參考文獻 96
第五章 附錄 99
一、晶體CIF check資料 100
二、ESI/APCI-MS資料 105
三、元素分析資料 115

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