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http://hdl.handle.net/11455/16456| DC Field | Value | Language |
|---|---|---|
| dc.contributor | 洪政雄 | zh_TW |
| dc.contributor | 葉鎮宇 | zh_TW |
| dc.contributor.advisor | 陳如珍 | zh_TW |
| dc.contributor.author | 方雅貞 | zh_TW |
| dc.contributor.author | Fang, Ya-Cheng | en_US |
| dc.contributor.other | 中興大學 | zh_TW |
| dc.date | 2007 | zh_TW |
| dc.date.accessioned | 2014-06-06T06:55:27Z | - |
| dc.date.available | 2014-06-06T06:55:27Z | - |
| dc.identifier | U0005-1208200603175200 | zh_TW |
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| dc.identifier.uri | http://hdl.handle.net/11455/16456 | - |
| dc.description.abstract | 論文摘要 六配位三價鐵卟啉具有重要的生物意義，受到不同軸配基的影響可以呈現各種不同的電子組態。含氮軸配基如咪唑（Im）等大都使其呈現典型低自旋（dxy2 dxz,yz3, S = 1/2）電子組態；強場軸配基、好的π接受者則可能導致不尋常低自旋（dxz,yz4 dxy1, S = 1/2）電子組態，並伴隨著大環的皺摺變形。已知皺摺變形使得金屬dxy軌域和大環a2u軌域對稱相同，可以發生鍵結作用，是形成不尋常低自旋（dxz,yz4 dxy1, S = 1/2）電子組態的主要原因。至於馬鞍型變形以及強場軸配基對六配位三價鐵卟啉電子組態的影響則是本論文的主題。 先前針對氰基錯合物[FeP(CN)2]-（P = TPP、TiPP、OETPP）的研究顯示，軸配基配位原子13CN的化學位移呈現明顯的差異，除了受電子組態的影響，同時也與大環的變形有關。文中進一步測得[Fe(OMTPP)(CN)2]- 之13CN化學位移為-2182 ppm，顯示馬鞍型變形程度增加，錯合物的磁方向性減少，與EPR結果相符。 已知馬鞍型變形導致卟啉大環a2u軌域能量上升，較易被氧化；而異氰基為好的π接受者，有利於低氧化態的穩定。當異氰基配位於馬鞍型三價鐵卟啉，是否可能產生不尋常的二價鐵卟啉π陽離子自由基，是個很耐人尋味的問題。本文中結合NMR與理論計算的分析深入探討一系列錯合物[FeP(CNtBu)2]+（P = TPP、TiPP、OMTPP、OETPP、OET(p-OMe)PP），顯示馬鞍型變形系統確實存在部分二價鐵卟啉π陽離子自由基電子組態的貢獻。延續這樣的思考邏輯，相信透過軸配基和卟啉大環的修飾，我們有機會使這種不尋常的電子組態更加穩定。論文中對亞磷酸鹽（P(OMe)3）軸配基的性質也做了初步的研究。 | zh_TW |
| dc.description.tableofcontents | 目錄 摘要 第一章 背景介紹 1-1 前言-------------------------------------------------------------------------------01 1-2 金屬卟啉簡介-------------------------------------------------------------------05 1-3 順磁核磁共振光譜與金屬卟啉的電子組態-------------------------------11 1-4 理論計算的應用----------------------------------------------------------------19 1-5 金屬卟啉錯合物的簡介-------------------------------------------------------22 1-6 低自旋三價鐵卟啉錯合物的簡介-------------------------------------------25 1-7 參考文獻-------------------------------------------------------------------------30 第二章 金屬卟啉錯合物的合成製備 2-1 儀器設備-------------------------------------------------------------------------37 2-2 使用藥品-------------------------------------------------------------------------37 2-3 Fe(por)ClO4系列錯化物的合成----------------------------------------------41 2-3-1 Fe(TPP)ClO4------------------------------------------------------------41 2-3-2 Fe(TiPP)ClO4-----------------------------------------------------------44 2-3-3 Fe(OMTPP)ClO4-------------------------------------------------------46 2-3-4 Fe(OETPP)ClO4--------------------------------------------------------51 2-4 [Fe(por)(tBuNC)2]+系列錯化物的製備--------------------------------------56 2-4-1 [Fe(TPP)(tBuNC)2]+----------------------------------------------------56 2-4-2 [Fe(TiPP)(tBuNC)2]+---------------------------------------------------57 2-4-3 [Fe(OMTPP)(tBuNC)2]+-----------------------------------------------58 2-4-4 [Fe(OETPP)(tBuNC)2]+------------------------------------------------59 CoII( ORTPP )+•X ( R = Me, Et; X = Cl, Br, I )的合成---------------------59 附錄13C -Labeling-tert-butylisocyanide之合成----------------------------60 2-5 [Fe(TPP)(P(OMe)3)2]+與FeП(TPP)(P(OMe)3)2之製備--------------------62 2-5-1 [Fe(TPP)(P(OMe)3)2]+-------------------------------------------------62 2-5-2 FeП(TPP)(P(OMe)3)2---------------------------------------------------62 附錄 Zn/Hg ( zinc amalgam ) 的合成方法---------------------------------63 2-6 [Fe(OMTPP)(CN)2] -錯化物的製備------------------------------------------64 2-6-1 [Fe(OMTPP)(CN)2]----------------------------------------------------64 附錄 TBA+13CN-- 13C enriched的合成方法-------------------------------64 2-6-2 [CoII(OMTPP)(CN)2]--------------------------------------------------64 2-7 參考文獻-------------------------------------------------------------------------65 第三章 三價鐵卟啉錯合物之研究與探討 3-1 [Fe(OMTPP)(CN)2]-錯化物的鑑定與分析----------------------------------67 3-2 [Fe(por)(tBuNC)2]+系列錯化物的鑑定與分析-----------------------------79 3-1-1 [Fe(TiPP)(tBuNC)2]+ ---------------------------------------------------67 3-1-2 [Fe(TPP)(tBuNC)2]+-----------------------------------------------------87 3-1-3 [Fe(OMTPP)(tBuNC)2]+------------------------------------------------96 3-1-4 [Fe(OETPP)(tBuNC)2]+------------------------------------------------103 3-1-5 [Fe(OET(p-OMe)PP)(tBuNC)2]+-------------------------------------112 3-2 [Fe(TPP)(P(OMe)3)2]+錯化物的鑑定與分析-------------------------------125 3-4 [Fe(OMTPP)(CN)2]-錯化物之結果與探討---------------------------------104 3-5 [Fe(por)(tBuNC)2]+系列錯化物之結果與討論-----------------------------139 （por = TPP，OMTPP，OETPP，OET(p-OMe)PP) 3-6 [Fe(por)(P(OMe)3)2]+錯化物結果與討論-----------------------------------178 3-7 結論-------------------------------------------------------------------------------189 3-8 參考文獻-------------------------------------------------------------------------190 圖表目錄 表目次 第一章 背景介紹 表1-1 [Fe(por)(CN)2]-之化學位移對核電子自旋密表-------------------------------27 第二章 金屬卟啉錯合物的合成製備 第三章 三價鐵卟啉錯合物之研究與探討 表3-1 [Fe(por)(CN)2]-之平衡常數( por = OMTPP、OETPP ) ---------------------71 表3-2 [Fe(OMTPP)(CN)2]-之不同溫度的化學位移----------------------------------74 表3-3 [Fe(TiPP)(tBuNC)2]+在不同溫度之化學位移對-------------------------------83 表3-4 [Fe(TPP)(tBuNC)2]+在不同溫度之化學位移----------------------------------94 表3-5 [Fe(TPP)(tBuNC)2]+在不同溫度之化學位移----------------------------------94 表3-6 [Fe(OETPP)(tBuNC)2]+在不同溫度之化學位移-----------------------------109 表3-7 [Fe(TPP)(P(OMe)3)2]+的不同溫度之化學位移-------------------------------118 表3-8 逆磁核磁共振光譜數據----------------------------------------------------------122 表3-9 EPR g Values of [Fe(por)(L)2]+ at 77 K-----------------------------------------123 表3-10 [Fe(por)(L)2]+之1H NMR化學位移------------------------------------------124 表3-11 [Fe(por)(L)2]+之13C & 31P NMR化學位移----------------------------------124 表3-12 Mulliken closed-shell（open-shell）Populations for the Iron(Ш) d orbitals in [Fe(OMTPP)(CN)2] -Complex for Unrestricted ADF Calculations --------------------------------------------------------------------------------------127 表3-13 [Fe(OMTPP)(CN)2]-之化學位移比對核電子自旋密度表----------------128 表3-14 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(CN)2]- D2d 2E-dpi （Karplus）------------------130 表3-15 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(CN)2]- D2d 2B2-dxy （Karplus）-----------------131 表3-16 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(CN)2]- D2d 2E-dpi （Mispelter）----------------132 表3-17 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(CN)2]- D2d 2B2-dxy （Mispelter）--------------132 表3-18 EPR g Values of [Fe(por)(CN)2]- at 4.2 K（CH2Cl2）---------------------134 表3-19 Orbital Overlaps between the Fragment Orbitals of [Fe(OMTPP)(CN)2]--2E D2d---------------------------------------------------------------------------------136 表3-20 [Fe(OMTPP)(CN)2]--2E--------------------------------------------------------136 表3-21 Orbital Overlaps between the Fragment Orbitals of [Fe(OMTPP)(CN)2]--2B2 D2d---------------------------------------------------------------------------------137 表3-22 [Fe(OMTPP)(CN)2]--2B2 D2d----------------------------------------------138 表3-23 Decompostion of the [Fe(por)(CN)2]- interaction Energy-----------------139 表3-24 Mulliken closed-shell（open-shell）Populations for the Iron(Ш) d orbitals in [Fe(OMTPP)(HNC)2]+ Complex for Unrestricted ADF Calculations -------------------------------------------------------------------------------------145 表3-25 Mulliken closed-shell（open-shell）Populations for the Iron(Ш) d orbitals in [Fe(OET(p-OH)PP)(HNC)2]+ Complex for Unrestricted ADF Calculations-----------------------------------------------------------------------145 表3-26 [Fe(por)(HNC)2]+之化學位移比對核電子自旋密度表 ------------------146 表3-27 [Fe(TiPP)(HNC)2]+之化學位移比對核電子自旋密度表 ----------------147 表3-28 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(TPP)(HNC)2]+ D2d dpi （Karplus）------------------------147 表3-29 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(TPP)(HNC)2]+ D2d a2u-dxy （Karplus）-------------------148 表3-30 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(TPP)(HNC)2]+ D2d dxy （Karplus）-----------------------148 表3-31 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(TPP)(HNC)2]+ D2d dpi （Mispelter）--------------------------149 表3-32 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(TPP)(HNC)2]+ D2d a2u-dxy （Mispelter）---------------------150 表3-33 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(TPP)(HNC)2]+ D2d dxy （Mispelter）-------------------------150 表3-34 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(HNC)2]+ D2d dpi （Karplus）-----------------------152 表3-35 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(HNC)2]+ D2d dxy-a1u （Karplus）------------------152 表3-36 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(HNC)2]+ D2d a2u （Karplus）----------------------153 表3-37 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(HNC)2]+ D2d dpi （Mispelter）---------------------154 表3-38 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(HNC)2]+ D2d dxy-a1u （Mispelter）----------------154 表3-39 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OMTPP)(HNC)2]+ D2d a2u （Mispelter）--------------------155 表3-40 [Fe(OMTPP)(HNC)2]+之化學位移比對核電子自旋密度表------------156 表3-41 [Fe(OMTPP)(HNC)2]+之化學位移比對核電子自旋密度表------------157 表3-42 [Fe(TiPP)(HNC)2]+-a2u-dxy（tBuNC → HNC）---------------------------159 表3-43 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d a1u-dxy （Karplus）--------------160 表3-44 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d dpi （Karplus）-------------------160 表3-45 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d dxy-a1u （Karplus）-------------------161 表3-46 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d a2u （Karplus）-------------------161 表3-47 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d a1u （Mispelter）-----------------162 表3-48 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d dpi （Mispelter）---------------------163 表3-49 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d dxy-a1u （Mispelter）----------------163 表3-50 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OETPP)(HNC)2]+ D2d a2u （Mispelter）------------------164 表3-51 [Fe(OETPP)(HNC)2]+ & [Fe(OETPP)(tBuNC)2]+之化學位移比對核電子自旋密度表-------------------------------------------------------------------------166 表3-52 不同電子組態a2u與HNC軌域組成表------------------------------------167 表3-53 [Fe(OETPP)(HNC)2]+之改變鍵長與核自旋密度表----------------------167 表3-54 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OET(p-OH)PP)(HNC)2]+ D2d dpi （Karplus）----------169 表3-55 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OET(p-OH)PP)(HNC)2]+ D2d dxy-a1u （Karplus）-----169 表3-56 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OET(p-OH)PP)(HNC)2]+ D2d a2u （Karplus）----------170 表3-57 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OET(p-OH)PP)(HNC)2]+ D2d dpi （Mispelter）--------171 表3-58 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OET(p-OH)PP)(HNC)2]+ D2d dxy-a1u （Mispelter）-----171 表3-59 Paramagnetic NMR Chemical Shift Analysis for 1H and 13C NMR [Fe(OET(p-OH)PP)(HNC)2]+ D2d a2u （Mispelter）--------172 表3-60 Orbital Overlaps between the Fragment Orbitals of [Fe(OMTPP)(HNC)2]+-dxy-----------------------------------------------------174 表3-61 [Fe(OMTPP)(HNC)2]+-dxy-----------------------------------------------------174 表3-62 Orbital Overlaps between the Fragment Orbitals of [Fe(OMTPP)(HNC)2]+-dxy-a1u-------------------------------------------------175 表3-63 [Fe(OMTPP)(HNC)2]+-dxy-a1u-------------------------------------------------175 表3-64 Orbital Overlaps between the Fragment Orbitals of [Fe(OMTPP)(HNC)2]+-dπ------------------------------------------------------176 表3-65 [Fe(OMTPP)(HNC)2]+-dπ------------------------------------------------------176 表3-66 Orbital Overlaps between the Fragment Orbitals of [Fe(OMTPP)(HNC)2]+-a2u-----------------------------------------------------177 表3-67 [Fe(OMTPP)(HNC)2]+-a2u-----------------------------------------------------177 表3-68 Decompostion of the [Fe(OMTPP)(HNC)2]+ interaction Energy--------178 表3-69 Mulliken closed-shell（open-shell）Populations for the Iron(Ш) d orbitals in [Fe(TPP)(P(OH)3)2]+Complex for Unrestricted ADF Calculations----------------------------------------------------------------------181 表3-70 [Fe(TPP)(P(OH)3)2]+之化學位移比對核電子自旋密度表--------------181 表3-71 Orbital Overlaps between the Fragment Orbitals of [Fe(TPP)(HNC)2]+-dxy D2d---------------------------------------------------------------------------------183 表3-72 [Fe(TPP)(HNC)2]+-dxy----------------------------------------------------------183 表3-73 Orbital Overlaps between the Fragment Orbitals of [Fe(TPP)(P(OH)3)2]+-dxz C2----------------------------------------------------------------------------------184 表3-74 [Fe(TPP)(P(OH)3)2]+-dxz-------------------------------------------------------185 表3-75 Orbital Overlaps between the Fragment Orbitals of [Fe(TPP)(P(OH)3)2]+-dxy-a2u C2--------------------------------------------186 表3-76 [Fe(TPP)(P(OH)3)2]+-dxy-a2u---------------------------------------------------187 表3-77 Decompostion of the [Fe(TPP)(P(OH)3)2]+ interaction Energy-----------189 表3-78 Decompostion of the [Fe(TPP)(HNC)2]+ interaction Energy--------------189 圖目次 第一章 背景介紹 圖1-1 血紅素的結構-------------------------------------------------------------------------2 圖1-2 血紅蛋白-------------------------------------------------------------------------------3 圖1-3 血紅素蛋白的構造-------------------------------------------------------------------4 圖1-4 卟啉的結構----------------------------------------------------------------------------5 圖1-5 卟啉化合物----------------------------------------------------------------------------6 圖1-7 非平面卟啉的結構-------------------------------------------------------------------8 圖1-8 變行卟啉大環a1u、a2u軌域合LUMO的相對能階---------------------------9 圖1-9 三價鐵卟啉d軌愈能階分裂及電子組態---------------------------------------10 圖1-10 -----------------------------------------------------------------------------------------14 圖1-11 Fe(TPP)等向位移對幾何因素作圖----------------------------------------------14 圖1-12 -----------------------------------------------------------------------------------------16 圖1-13 -----------------------------------------------------------------------------------------17 圖1-14 卟啉的基本結構-------------------------------------------------------------------22 圖1-15 pyrrole合成(a)Ono, (b)Lightner的方法----------------------------------------24 第二章 金屬卟啉錯合物的合成製備 圖2-1 TPPH2的合成--------------------------------------------------------------------------41 圖2-2 TiPPH2的合成-------------------------------------------------------------------------44 圖2-3 OMTPPH2合成流程圖--------------------------------------------------------------46 圖2-4 OETPPH2合成流程圖---------------------------------------------------------------51 第三章 三價鐵卟啉錯合物之研究與探討 圖3-1 Bu4NCN滴定Fe(OMTPP)Cl之UV-Vis光譜(CHCl3)----------------------67 圖3-2 Bu4NCN滴定Fe(OMTPP)Cl(a) 4~5配位, (b) 5~6配位之UV-Vis光譜(CH2Cl2) ----------------------------------------------------------------------------68 圖3-3 Bu4NCN(l)滴定Fe(OMTPP)Cl之400 MHz 1H NMR光譜圖(CDCl3) ----------------------------------------------------------------------------------------72 圖3-4 [Fe(OMTPP)(CN)2]-之變溫300 MHz 1H NMR光譜圖(CD2Cl2) -----------------------------------------------------------------------------------------73 圖3-5 [Fe(OMTPP)(CN)2]-之化學位移對T-1之關係圖-----------------------------74 圖3-6 [Co(OMTPP)(CN)2]2-之室溫時400 MHz 1H NMR光譜圖(CDCl3) ----------------------------------------------------------------------------------------75 圖3-7 [Fe(OMTPP)(13CN)2]-之室溫時300 MHz 13C NMR光譜圖(CD2Cl2) ----------------------------------------------------------------------------------------76 圖3-8 [Fe(OMTPP)(CN)2]-之室溫時300 MHz 13C NMR光譜圖(CD2Cl2) (a) proton broad band decoupled, (b) off resonance decoupled -----------------------------------------------------------------------------------------77 圖3-9 [Co(OMTPP)(CN)2]2-之室溫時400 MHz 13C NMR光譜圖(CDCl3) ----------------------------------------------------------------------------------------78 圖3-10 (a) Fe(TiPP)ClO4, (b) [Fe(TiPP)(tBuNC)2]+之UV-Vis光譜(CH2Cl2) ---------------------------------------------------------------------------------------79 圖3-11 tBuNC(l)滴定Fe(TiPP)ClO4之200 MHz 1H NMR光譜圖(CDCl3) ---------------------------------------------------------------------------------------80 圖3-12 [Fe(TiPP)(tBuNC)2]+之室溫時400 MHz 1H NMR光譜圖(CDCl3) ---------------------------------------------------------------------------------------81 圖3-13 [Fe(TiPP)(tBuNC)2]+之變溫300 MHz 1H NMR光譜圖(CD2Cl2) ---------------------------------------------------------------------------------------82 圖3-14 [Fe(TiPP)(tBuNC)2]+之化學位移對T-1關係圖(CD2Cl2) ------------------83 圖3-15 室溫時[Fe(TiPP)(tBuNC)2]+之600 MHz 13C NMR光譜圖(CD2Cl2) ---------------------------------------------------------------------------------------84 圖3-16 [Fe(TiPP)(tBuNC)2]+之77 K EPR光譜圖(a) CH2Cl2, (b) CHCl3 ---------------------------------------------------------------------------------------85 圖3-17 [Fe(TiPP)(tBuNC)2]+的μeff與1/χ對T作圖(at 3000 G) -------------------85 圖3-18 (a) Fe(TPP)ClO4, (b) [Fe(TPP)(tBuNC)2]+之UV-Vis光譜(CH2Cl2) ---------------------------------------------------------------------------------------87 圖3-19 tBuNC(l)滴定Fe(TPP)ClO4之400 MHz 1H NMR光譜圖(CDCl3) ---------------------------------------------------------------------------------------88 圖3-20 [Fe(TPP)(tBuNC)2]+室溫時之600 MHz 1H NMR光譜圖(CDCl3) --------------------------------------------------------------------------------------89 圖3-21 [Fe(TPP)(tBuNC)2]+之部分氫原子的化學位移對T-1關係圖(CD2Cl2) ----------------------------------------------------------------------------------------89 圖3-22 [Fe(TPP)(tBuNC)2]+室溫時之600 MHz 13C NMR光譜圖(CDCl3) (a) proton broad band decoupled, (b) off resonance decoupled. ----------------------------------------------------------------------------------------91 圖3-23 [Fe(TPP)(tBuNC)2]+之600 MHz 13C NMR光譜圖 (a) 室溫時meso-13C (CDCl3), (b) -50 ºC之tBuN13C (CD2Cl2 ) ----------------------------------------------------------------------------------------91 圖3-24 [Fe(TPP)(tBuNC)2]+之變溫600 MHz 13C NMR光譜圖(a) CD2Cl2, (b) CDCl3--------------------------------------------------------------------------------92 圖3-25 [Fe(TPP)(tBuNC)2]+之化學位移對T-1關係圖 (a) CD2Cl2,(b) CDCl3 ----------------------------------------------------------------------------------------93 圖3-26 [Fe(TPP)(tBuNC)2]+之77 k EPR光譜圖(a) CH2Cl2, (b) CHCl3 ---------------------------------------------------------------------------------------94 圖3-27 [Fe(TPP)(tBuNC)2]+的μeff與1/χ對T作圖----------------------------------95 圖3-28 (a) Fe(OMTPP)ClO4,(b) [Fe(OMTPP)(tBuNC)2]+之UV-Vis光譜(CH2Cl2) --------------------------------------------------------------------------------------96 圖3-29 tBuNC(l)滴定Fe(OMTPP)ClO4之400 MHz 1H NMR光譜圖(CDCl3) --------------------------------------------------------------------------------------97 圖3-30 [Fe(OMTPP)(tBuNC)2]+之300 MHz 1H NMR光譜圖(CD2Cl2) (a) -50 ºC,(b) 室溫時-------------------------------------------------------------98 圖3-31 [Fe(OMTPP)(tBuNC)2]+之部分氫原子的化學位移對T-1關係圖(CD2Cl2) --------------------------------------------------------------------------------------98 圖3-32 Co(OMTPP)(tBuNC)2之室溫時400 MHz 1H NMR光譜圖(CDCl3) --------------------------------------------------------------------------------------99 圖3-33 [Fe(OMTPP)(tBuNC)2]+之室溫時600 MHz 13C NMR光譜圖(CD2Cl2) (a) proton broad band decoupled, (b) off resonance decoupled --------------------------------------------------------------------------------------100 圖3-34 Co(OMTPP)(tBuNC)2之室溫時400 MHz 1H NMR光譜圖(CDCl3) -------------------------------------------------------------------------------------101 圖3-35 [Fe(OMTPP)(tBuNC)2]+之77 K EPR光譜圖(a) CH2Cl2,(b) CHCl3 ------------------------------------------------------------------------------------102 圖3-36 (a) Fe(OETPP)ClO4,(b) [Fe(OETPP)(tBuNC)2]+之UV-Vis光譜(CH2Cl2) ------------------------------------------------------------------------------------103 圖3-37 tBuNC(l)滴定Fe(OETPP)ClO4之400 MHz 1H NMR光譜圖(CDCl3) ------------------------------------------------------------------------------------104 圖3-38 [Fe(OETPP)(tBuNC)2]+之室溫時300 MHz 1H NMR光譜圖(CD2Cl2) --------------------------------------------------------------------------------------105 圖3-39 [Fe(OETPP)(tBuNC)2]+之氫原子化學位移對T-1關係圖(CD2Cl2) -------------------------------------------------------------------------------------105 圖3-40 Co(OETPP)(tBuNC)2之室溫時400 MHz 1H NMR光譜圖(CDCl3) --------------------------------------------------------------------------------------106 圖3-41 [Fe(OETPP)(tBuNC)2]+之室溫時300 MHz13C NMR光譜圖(CD2Cl2) (a) proton broad band decoupled, (b) off resonance decoupled. --------------------------------------------------------------------------------------107 圖3-42 [Fe(OETPP)(tBuN13C)2]+-50 ºC時600 MHz 13C NMR光譜圖(CD2Cl2) --------------------------------------------------------------------------------------107 圖3-43 [Fe(OETPP)(tBuNC)2]+之變溫600 MHz 13C NMR光譜圖(CD2Cl2) --------------------------------------------------------------------------------------108 圖3-44 [Fe(OETPP)(tBuNC)2]+之化學位移對T-1關係圖-------------------------109 圖3-45 Co(OETPP)(tBuNC)2之室溫時300 MHz 1H NMR光譜圖(CDCl3) --------------------------------------------------------------------------------------110 圖3-46 [Fe(OETPP)(tBuNC)2]+之77 K EPR光譜圖(a) CH2Cl2,(b) CHCl3 --------------------------------------------------------------------------------------110 圖3-47 [Fe(OET(p-OMe)PP)(tBuNC)2]+之UV-Vis光譜(CH2Cl2) --------------------------------------------------------------------------------------112 圖3-48 [Fe(OET(p-OMe)PP)(tBuNC)2]+之-50 ºC時600 MHz 1H NMR光譜圖(CD2Cl2) --------------------------------------------------------------------------112 圖3-49 [Fe(OET(p-OMe)PP)(tBuNC)2]+之-50 ºC時600 MHz 13C NMR光譜圖(CD2Cl2) proton broad band decoupled--------------------------------113 圖3-50 [Fe(OET(p-OMe)PP)(tBuNC)2]+之室溫時600 MHz 13C NMR光譜圖(CD2Cl2) off resonance decoupled. ------------------------------------114 圖3-51 [Fe(OET(p-OMe)PP)(tBuNC)2]+之77 K EPR光譜圖(CH2Cl2) --------------------------------------------------------------------------------------114 圖3-52 (a) Fe(TPP)ClO4,(b) [Fe(TPP)(P(OMe)3)2]+之UV-Vis光譜(CH2Cl2) ------------------------------------------------------------------------------------115 圖3-53 P(OMe)3(l)滴定Fe(TPP)ClO4之400 MHz 1H NMR光譜圖(CDCl3) --------------------------------------------------------------------------------------116 圖3-54 [Fe(TPP)(P(OMe)3)2]+之室溫時400 MHz 1H NMR光譜圖(CD2Cl2) --------------------------------------------------------------------------------------117 圖3-55 [Fe(TPP)(P(OMe)3)2]+之變溫300 MHz 1H NMR光譜圖(CD2Cl2) --------------------------------------------------------------------------------------117 圖3-56 [Fe(TPP)(P(OMe)3)2]+之化學位移對T-1之關係圖------------------------118 圖3-57 Fe | zh_TW |
| dc.language.iso | en_US | zh_TW |
| dc.publisher | 化學系所 | zh_TW |
| dc.subject | Iron(III) porphyrins | en_US |
| dc.subject | 三價鐵卟啉 | zh_TW |
| dc.title | 強場軸配基對六配位三價鐵卟啉電子組態的影響 | zh_TW |
| dc.title | The Effect of Strong Field Axial Ligands on the Electronic Configuration of Six-Coordinate Iron(III) Porphyrins. | en_US |
| dc.type | Thesis and Dissertation | zh_TW |
| item.openairetype | Thesis and Dissertation | - |
| item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
| item.fulltext | no fulltext | - |
| item.grantfulltext | none | - |
| item.languageiso639-1 | en_US | - |
| item.cerifentitytype | Publications | - |
| Appears in Collections: | 化學系所 | |
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