我們合成一系列雙取代芳香環之雜環分子，3,6-disubstituted-1,2,4,5-tetrazine與3,6-disubstituted-pyridazine，及其銥金屬錯合物，Ir(Rdppa)3 (Rdppa = di(R'-phenyl)pyridazine, R'=2-Cl, 3-Cl, 4-Cl, 3-Br, 4-Me)與Ir(pdppa)3 (pdppa = 3,4,6-triphenylpyridazine)，此系列分子活化苯環離去氫原子，與銥(III)金屬離子反應形成triscyclometalated中性化合物。由X-ray的單晶結構可知錯合物的構形為trans-Ir(dppa)3，其未鍵結金屬之苯環與相鄰分子之未鍵結苯環具有π-πstacking作用力，使得分子向不同方向延伸堆疊具高對稱性。錯合物的電子吸收光譜具有配位子之π-π*、1MLCT以及屬於自旋禁阻3MLCT之電子躍遷，錯合物具有不錯的磷光放射，其放光波長介於533 nm( Ir(4Cldppa)3 )至575 nm( Ir(pdppa)3 )間，此系列配位基之LUMO能階分佈於較缺電子的pyridazine環上，而HOMO能階則分佈於電子密度較高的芳香環上，藉由對苯環作拉電子基的修飾將降低HOMO能階，發現放光波長產生藍位移，而弱推電子基(-CH3)對放射波長的影響並不明顯，芳香環的修飾降低LUMO能階，使得放光波長紅位移了20 nm。錯合物吸收光譜與放射光譜之stokes shift值均小於100 nm，因此推測這一系列銥錯合物之磷光放射主要源自於3MLCT激發態所貢獻。錯合物的激發態生命期介於0.91 µs( Ir(3Brdppa)3 )至2.9 µs( Ir(4Medppa)3 )間，量子產率最高為Ir(4Cldppa)3之0.429，最低為Ir(dppa)3之0.069。錯合物均具有一可逆的氧化還原峰，苯環有拉電子基的取代，將有效地提高其氧化電位，推電子基之取代則發現其氧化電位降低，由於錯合物之氧化發生於銥中心金屬與苯環間，是故在pyridazine環上苯環的修飾對錯合物的氧化電位並無明顯的影響。放光波長的紅藍位移趨勢取決於淨能隙的變化，當拉電子基的取代，使得HOMO下降的程度大於LUMO，將造成淨能隙增加而使放光波長產生藍位移。由3,6-disubstituted-1,2,4,5-tetrazine衍生得一系列新的H形結構分子，1,4-bis(3,6-di-R"-pyridazin-4-yl)benzene (R"= phenyl、3-chlorophenyl與3-bromophenyl)，X-ray的單晶結構發現1,4-bis(3,6-diphenylpyridazin-4-yl)-benzene分子間具有π-π stacking作用力使得分子交錯堆疊形成孔狀結構，孔徑約6.3 Å x 6.9 Å。3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine (H2boptz)、3,6-bis(2-hydroxyphenyl)pyridazine (H2boppa)與3,5-bis(2-hydroxyphenyl)-1,3,4-oxadiazole (H2bopoa)為新的一系列具有雙苯酚取代之雜環分子，兩苯酚之OH與中間雜環之氮原子均具有氫鍵作用力，使得分子之去質子化較為不易，H2boptz之pKa值為12.7。

The photophysical property of tris-cyclometalated complexes of Ir(III) make them useful for several photonic applications. The attraction of these complexes for such applications comes from their long excited-state lifetime and high luminescent efficiencies. The Synthesis, structure, electrochemistry, and photophysics of the tris-cyclometalated Ir(III) complexes are reported. Reaction of the Ir(acetylacetonate)3 with 3,6-disubstituted-pyridazine (Rdppa, 3,6-di(R’-phenyl)pyridazine, R’=2-Cl, 3Cl, 4-Cl, 3-Br, 4-Me) and 3,4,6-triphenylpyridazine (pdppa) ligands forms the present compounds. The Ir-C and Ir-N bonds with trans configuration is observed for the phenylpyridazine-based complexes. The compounds have intense absorption bands in the UV region assigned into π-π＊ transitions and a weaker MLCT transition that extend to the visible region. The tris-cyclometalated Ir(III) complexes exhibit intense emission at room temperature, with emission characteristic of phosphorescence from a 3MLCT triplet state. The complexes show reversible reduction-oxidation process. The substitution of electron-withdrawing group at phenyl ring resulted in the hypsochromic shift in the emission wavelength since lower HOMO. Electronegative nitrogen and enlarging the π-conjugation exert bathochromic shift on the emission wavelength since lower LUMO.
A microporous material constructed by π-π interaction of a twisted H-shape poly-aromatic molecule, 1,4-bis(3,6-diphenylpyridazin-4-yl)benzene was synthesized by the reaction of 1,4-diacetylbenzene and 3,6-diphenyl-1,2,4,5tetrazine. The intermolecular distances between the various aromatic rings are within the range of 3.4~3.7 Å which indicate the intermolecular π-π stacking interaction. Hexagonal channels with pore width 6.3 Å x 6.9 Å along the c axis were observed. Interstitial water and MeOH molecules were located within each porous channel.
3,6-disubstituted-1,2,4,5-tetrazine moieties have become popular as efficient electronic spacers in dinuclear and polynuclear systems, due to the fact that the tetrazine-based low-lying π* orbital conveys strong π-accepting characteristics, leading to excellent electronic communication between the metal termini. A serial of diphenolate ligands, 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine (H2boptz), 3,6-bis(2-hydroxyphenyl) pyridazine (H2boppa) and 3,5-bis(2-hydroxyphenyl)-1,3,4-oxadiazole (H2bopoa) were synthesized and characterized, and the ligand H2boptz contain phenolate donors and a central tetrazine π-acceptor function. The pKa value of H2boptz is 12.7.

目  錄
中文摘要
英文摘要
目錄………………………………………………...I
圖目錄…………………………………………..III
表目錄……………………………………………...VI
第一章 緒論………………..…………………….1
1-1.	d6族金屬錯合物之光物理特性……….1
1-2.	螢光與磷光………………………………1
1-3.	發光d6族金屬錯合物之進展…………4
1-4.	銥金屬錯合物之發展背景……………...5
1-5.	研究動機…………………………..27
第二章 合成與結構……………..……...28
2-1.	配位子之合成………………….28
2-2.	銥錯合物之合成………………..33
2-3.	錯合物之結構………………...36
第三章 光物理性質…………………………..42
3-1.	溶液態吸收與放射光譜………………...42
3-2.	固態放射光譜……………………………53
3-3.	量子產率……………………………...55
第四章 電化學性質……………..60
第五章 雙酚取代tetrazine、pyridazine與oxadiazole分子…65
5-1.	緒論………………………...65
5-2.	合成方法與討論…………….……….66
5-3.	X-ray單晶結構…………………….70
5-4.	光物理性質……………….………...75
5-5.	酸鹼性質…………………...76
第六章 孔洞結構分子1,4-bis(3,6-
diphenylpyridazin-4-yl)benzene及其衍生物……...79
6-1.	緒論……………………………………79
6-2.	化合物之合成…………………………..80
6-3.	X-ray單晶結構…………………………81
6-4.	1,4-bis(3,6-diphenylpyridazin-
4-yl)benzene之衍生物……...83
6-5.	熱穩定性質探討………………………..86
第七章 實驗部分………………………………88
7-1.	試劑……………………………….88
7-2.	實驗步驟………………………….88
7-2-1. 配位基之合成………………………….88
7-2-2. 銥錯合物之合成…………………….94
7-3.	物理性質測定方法…………………….101
結論………………………………………………...104
參考文獻…………………………………..106
附錄………………………………115
圖 目 錄
圖1-1. 螢光(F)與磷光(P)簡圖………………………...2
圖1-2. 激發態電子去活化的形式………………………...3
圖1-3. ortho-metalated配位子ppy與bzq…………….…5
圖1-4. 銥雙體錯合物(C^N)2Ir(μ-Cl)Ir(C^N)2…………..6
圖1-5. tris-cyclometalated銥錯合物Ir(ppy)3之合成流程圖…6
圖1-6. 配位子hat及其銥錯合物……………………..7
圖1-7. MLCT與SBLCT電子轉移機制………………….8
圖1-8. fac-Ir(thpy)3結構圖…………………………9
圖1-9. 混配位子型銥錯合物…………………………...9
圖1-10. 混配位子型銥錯合物………………………...10
圖1-11. 不同官能基取代之tris-cyclometalated銥錯合物……11
圖1-12. 含fluorene官能基之銥錯合物…………………….12
圖1-13. thiophene與isoquinoline系列之
tris-cyclometalated銥錯合物…………………………...13
圖1-14. facial型與meridional型tris-cyclometalated銥錯合物….13
圖1-15. 含triazolyl pyridine銥錯合物之合成流程…………...14
圖1-16. 不同位置甲基修飾之tris-cyclometalated銥錯合物……16
圖1-17. 具quinoxaline之銥錯合物…………………………...17
圖1-18. Ir(ppy)3之修飾放光波長途徑………………….……...17
圖1-19. Ir(ppy)3之修飾與放光波長變化…………………...18
圖1-20. Ir(ppy)3之修飾與放光波長變化……………………...19
圖1-21. N-pyrazolyl與N-heterocyclic carbene系列銥錯合物…….20
圖1-22. a.錯合物Ir(ppz)3 (T1)與Ir(flz)3 (T1’)之輻射與非輻射能階b.carbene錯合物Ir(C^C:)3與Ir(ppz)3之非輻射能階相對關係…21
圖1-23. tris-cyclometalated之carbene銥錯合物…………...22
圖1-24. phenylpyrazolyl與diimine混配位子型
bis-cyclometalated銥錯合物…………………………...22
圖1-25. BlueJ、PVK、Ir(PBPP)3與Ir(PIQ)3之分子結構……….24
圖1-26. 雙核cyclometalated錯合物……………..……26
圖2-1. 配位基dppa之合成………………………….31
圖2-2. 配位基2Cldppa ~ 4Medppa之合成……………….32
圖2-3. 銥錯合物之合成………………………………….35
圖2-4. 錯合物fac-Ir(dppa)3之單晶結構………………...36
圖2-5. 錯合物Ir(dppa)3分子間之π-π stacking………38
圖2-6. 錯合物Ir(dppa)3之分子間堆疊……………………39
圖2-7. 錯合物Ir(dppa)3沿b軸之分子堆疊……………….39
圖2-8. 錯合物Ir(dppa)3沿c軸之分子堆疊………………..40
圖2-9. 錯合物fac-Ir(pdppa)3之單晶結構……………...…41
圖2-10. 錯合物Ir(pdppa)3之分子堆疊圖………………...41
圖3-1. 錯合物Ir(dppa)3與配位子dppa之UV/Vis吸收光譜圖…42
圖3-2. 錯合物Ir(dppa)3 ~ Ir(pdppa)3之UV/Vis吸收光譜……43
圖3-3. 錯合物Ir(dppa)3 ~ Ir(pdppa)3之放射光譜………….44
圖3-4. 錯合物fac-Ir(F2ppy)3相對於其它銥錯合物之放射光譜…45
圖3-5. fac-Ir(F3ppy)3與fac-Ir(F4ppy)3結構…………………46
圖3-6. 錯合物Ir(ppz)3與Ir(46dfppz)3結構………………47
圖3-7. 錯合物Ir(dppa)3之3MLCT吸收光譜與放射光譜……52
圖3-8. 錯合物Ir(dppa)3於不同激發波長之放射光譜……52
圖3-9. 銥錯合物之固態放射光譜………………………53
圖3-10. Ir(dppa)3與標準品[Ru(bpy)3](PF6)2
在氰甲烷溶劑中之吸收光譜…………………57
圖3-11. Ir(dppa)3與標準品[Ru(bpy)3](PF6)2
在氰甲烷溶劑中之放射光譜………………58
圖3-12. 錯合物Ir(dppa)3之激發態生命期…….58
圖4-1. 錯合物之循環伏安電位圖………………..62
圖4-2. 錯合物之HOMO-LUMO能階圖………………...63
圖5-1. 2-hydroxyphenyl衍生錯合物………………..66
圖5-2. 2-hydroxybenzonitrile與聯胺之反應流程圖………..66
圖5-3. H2boptz之單晶結構圖…………………………70
圖5-4. H2boppa之單晶結構圖………………………...71
圖5-5. H2bopoa (a)之單晶結構圖…………………...72
圖5-6. 2-(2,3-diaza-4-(2-hydroxyphenyl)buta-
1,3-dienyl)-phenol (b)之單晶結構圖……………….73
圖5-7. 2-hydroxy-N'-(propan-2-ylidene)benzohydrazide
 (c) (左)與2-hydroxybenzaldehyde hydrazone
 (d) (右)之單晶結構圖…...73
圖5-8. 3-(2-hydroxyphenyl)-5,6-
diphenyltriazine之單晶結構圖……...74
圖5-9. 3-(2-hydroxyphenyl)-5,6-
diphenyltriazine之堆疊圖…….……..74
圖5-10. H2boptz、H2boppa與H2bopoa之
UV/Vis吸收光譜圖………...75
圖5-11. 7.51x10-6 M之H2boptz以TBAOH滴定之UV-Vis光譜圖.…76
圖5-12. 7.51x10-6 M之H2boptz以TBAOH滴定之UV-Vis光譜圖….77
圖5-13. 354 nm與447nm吸收峰之log(Ai-A/A-Af)對pH值作圖…….78
圖6-1. 1,4-bis(3,6-diphenylpyridazin-4-yl)benzene之X-ray單晶結構..81
圖6-2. 1,4-bis(3,6-diphenylpyridazin
-4-yl)benzene之ORTEP圖及標號示意圖………………….81
圖6-3. 分子內環與環間之dihedral angle…………….82
圖6-4. 沿著a、b與c軸之分子堆疊…………………………82
圖6-5. 沿著c軸之分子堆疊Space-filling圖………...83
圖6-6. d3ClL與d3BrL之X-ray單晶結構……………..83
圖6-7. d3ClL與d3BrL之沿b軸分子堆疊………………84
圖6-8. d3ClL之沿b軸分子堆疊圖………………...85
圖6-9. d3BrL之沿b軸分子堆疊圖………………...86
圖6-10. 1,4-bis(3,6-diphenylpyridazin-4-
yl)benzene之熱重分析圖…..87
表 目 錄
表2-1. 錯合物Ir(dppa)3晶體之鍵長與鍵角數據………..37
表3-1. 錯合物之吸收與放光性質……………………….44
表3-2. 錯合物之溶液態與固態之放光性質…………...54
表3-3. 常見的螢光參考標準品………………………….56
表3-4. 錯合物之量子效率、生命期、輻射與
非輻射衰減速率常數….59
表4-1. 錯合物之氧化電位差、能量間隙、HOMO與LUMO能階……62
表5-1. H2boptz與H2boppa晶體之鍵長與鍵角數據…………………71
表5-2. 化合物之吸收與放光性質………………………….75

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