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研究生:洪欣儀
研究生(外文):Hung, Shin-Yi
論文名稱:混合配位基 Dipyrrinato/2,2'-Bipyridine 釕二價錯鹽的合成、電化學、吸收及冷光特性
論文名稱(外文):Characteristics of the Mixed Ligand Dipyrrinato/2,2'-Bipyridine Ru(II) Complexes: Syntheses, Electrochemistry, Absorption and Luminescence
指導教授:陳元璋
指導教授(外文):Chen, Yuan-Jang
口試委員:李國安陳信允
口試委員(外文):Lee, Gon-AnnChen, Hsing-Yin
口試日期:2012-06-14
學位類別:碩士
校院名稱:輔仁大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:82
中文關鍵詞:dipyrrin能量轉移
外文關鍵詞:dipyrrin
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本研究工作中主要以合成一系列 [Ru(bpy)2(Ar-dipy)]+ 錯鹽,其中 bpy = 2,2'-聯吡啶 (2,2'-bipyridine)、dipy = dipyrrin,Ar = Ph, py 和 4-Ph-NO2,並利用其電化學、吸收和放射光譜以了解單核鹽中影響其光物理特性,其中包含單重態至三重態 MLCT (Metal to ligand charge transfer) 系統內的能量轉移及三重態 MLCT 的磷光現象,此為以往文獻未曾報導的新發現。並將光譜數據與文獻及計算化學比較,得知此系列錯鹽在 21800 ~ 21600 cm-1 (459 ~ 463 nm) 範圍皆具有一個為 dipyrrin pi-pi* 的強吸收,另一較 broad 的吸收峰約在 19700 ~ 19300 cm-1 (510 ~ 520 nm) 為 Ru(II) 到 bpy 的 MLCT 吸收,而在 18000 ~ 15000 cm-1 (560 ~ 670 nm) 低能量吸收範圍的邊坡中可能包含了 Ru(II) 軌域到 dipyrrin pi* 軌域,及部分由 Ru(II) 到 dipyrrin + bpy 混成 pi* 軌域的 MLCT 吸收;而我們首次測量到此系列錯鹽3MLCT 磷光光譜。
The lowest energy metal-to-ligand charge transfer (MLCT) transition absorption bands found that series of [Ru(bpy)2(Ar-dipy)]+ (bpy = 2,2'- bipyridine, dipy = dipyrrin and Ar= Ph, py, 4-Ph-NO2) feature a weak Ru(II) to dipyrrin-pi* absorption on the low energy side of its absorption envelopes. Using the electrochemistry and spectral results compared with DFT calculations of the early works. We proposed the intense narrow band (hnmax = 21800 cm-1) which can be attributed to pi-pi* transition of the dipyrrin ligand, and the broader curves maximum at 19300 cm-1 can be attributed to Ru(II) to bpy-pi* of MLCT transition. In this work, we considered the lowest energy region band curve ranging between 18000 ~ 15000 cm-1 which may attribute to Ru(II) to dipyrrin-pi* orbital and part of Ru(II) to the mixing dipyrrin and bpy-pi* orbital of MLCT transitions. The 77 K broad emission curves maximun ranging between 13000 ~ 8000 cm1 should be a remarkable observations of the 3MLCT emission of the Rudipyrrin series.
目錄
謝誌 ii
摘要 vi
Abstract vii
第一章、前言
第一節、Fundamental Bases
1. 導論 1
2. Fundamental Properties of the Ru(II) Polypyridine Complexes 1
3. Superexchange Model 2
第二節、The BODIPY and Dipyrrinato Complexes Properties
1. Fundamental Properties 5
2. Synthesis of Dipyrrins and BODIPY 6
3. Structural Control of the Photophysis of BODIPY 7
4. HeavyAtom Effect on BODIPY 11
5. Dipyrrinato MixedLigand Ru(II) Complexes 11

第二章、實驗部分
第一節、實驗儀器及條件 15
第二節、實驗藥品及純化 17
第三節、實驗步驟與光譜數據 19

第三章、結果
第一節、Syntheses of Meso-Aryl Dipyrrinato Bis(bipyridine) Ru(II) Complexes 28
第二節、X-ray Single Crystal Diffraction Studies 29
第三節、Electrochemical Studies 30
第四節、UV/vis Absorption Studies 31
第五節、Emission Studies 32

第四章、討論
第一節、Xray Single Crystal Diffraction 34
第二節、Electrochemistry 35
第三節、Absorption and Luminescence 36

第五章、結論 39

第六章、參考文獻 40

Appendix A NMR Spectrometry 43
Appendix B Mass Spectrometry and Data 55
Appendix C X-ray Single Crystal Diffraction Data 64
Appendix D Cyclic Voltammogram 68
Appendix E Emission Spectrum 69
Appendix F Lifetime Spectrum and Data 70
Appendix G Absorption and Gaussian Bandshapes Spectrum 71

圖索引
Figure 1. Ligand pi* mediated superexchange coupling. 3
Figure 2. Ligand pi mediated superexchange coupling. 4
Figure 3. Cyclic voltammograms of compounds 2a-2c 10
Figure 4. Estimated energy level diagram of 8-10. 13
Figure 5. UV/vis spectra of 11b (in CH3OH). 14
Figure 6. Basic architecture and atom numbering of a [Ru(Ph-NO2-dipy)](PF6) without anion. 29
Figure 7. Cyclic voltammogram of [Ru(Ar-dipy)]+ complexes. 30
Figure 8. Absorption spectrum of [Ru(Ar-dipy)]+ series (in AN). 31
Figure 9. Emission spectrum of [Ru(py-dipy)]+ complex. 33
Figure 10. Basic architecture and atom numbering of (a) [Ru(Ph-NO2-
Figure 11. Low energy absorption band and Grams32 fit for [Ru(Ph-dipy)]+ in acetonitrile. 36
________________________________________
Chart 1. Numbering system for dipyrrins and BODIPY 5
Chart 2. Photophysis data and molecular structures of BODIPY compounds 8
Chart 3. Molecular structures of BODIPY compounds 10
Chart 4. Molecular structures of complexes 3-6 11
Chart 5. Structure of free ligands and metal complexes 7-10. 12
________________________________________
Scheme 1. Sythetic Route to complexes [11a]+ and 11b 13
Scheme 2. Sythetic Route to complexes [Ru(Ar-dipy)]+ 28 
表索引
Table 1. Selected bond lengths and dihedral angles for [Ru(Ph-NO2-dipy)](PF6). 29
Table 2. Half-Wave Potential of the Complexes 31
Table 3. UV/vis absorption data of the [Ru(Ar-dipy)]+ Complexes 32
Table 4. Emission and lifetime data for the [Ru(Ar-dipy)]+ Complexes 33
Table 5. The Gaussian fit by the Grams32 for [Ru(Ar-dipy)]+ complexes 37
Table 6. Select photophysical data for RuII complexes and related literature complexes 37


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