臺灣博碩士論文加值系統

2-苯基吡啶(2-phenylpyridine)，近年來在無機化學是相當熱門的螯合劑，其衍生物與過渡金屬所合成出來的金屬錯合物為發展主流並在最近幾年學術界熱門討論。除了過渡金屬之外，2-苯基吡啶之衍生物也可與芳香族化合物反應形成獨特的複合體，例如與糖精反應可合成出糖精鹽類。本篇論文主要探討利用本實驗室改良的2-苯基吡啶，在苯基4號碳位置上導入不同長度的短氟鏈，合成出含不同短氟鏈的金錯合物和糖精鹽類，並探討其結構的差異。本論文使用2-[(4-bromomethyl)phenyl]pyridine當前驅物，成功合成出一系列短氟鏈2-苯基吡啶取代基為輔助配體的金錯合物和糖精鹽類
〔(ppy-CH2OCH2-Rf)AuCl2〕和氟鏈糖精鹽(ppyRf-Saccharinate) (Rf = CF3、CF2CF2H、CF2CF3、CF2CF2CF3、CF2CF2CF2CF2H)，藉由 NMR、FT-IR、ESI等來鑑定之。有機材料的特性對於元件的光電表現有很大的影響，本論文的新型含氟鏈金錯合物與糖精鹽類，因為引進了氟鏈，進而擁有撥水性和抗氧性，這些性質使得這些新型金錯合物和糖精鹽類成為不錯的發光材料。

2-phenyl pyridine is a very popular ligand in inorganic chemistry in recent years. The derivative can be reacted with transition metal to become a metal complex. These metal complexes have been popular and discussed in academic in recent years. Except for metal complexes, the derivative also can be reacted with aromatic compounds to become a unique complex. For instance, saccharin reacts with the derivative to become saccharinate. This thesis is mainly to introduce different lengths of short fluorinated chains, synthesize gold metal complexes and saccharinate with different short fluorinated chains, and discuss the differences in luminescent properties.
2-[(4-bromomethyl)phenyl]pyridine was used as a precursor to synthesize a series of gold complexes and saccharinate with short fluorinated 2-phenylpyridine substituent as an ancillary ligand ppyRf-AuCl2 and ppy-Rf-Saccharin ( Rf = CF3, CF2CF2H, CF2CF3, CF2CF2CF3, CF2CF2CF2CF2H), identified by NMR, FT-IR and ESI. The photoelectric performance of components is influenced by characteristics of organic materials. These novel fluorine-containing gold complexes and saccharinate in this thesis have water repellency and antioxidant. These properties make these new gold complexes and saccharinate good light emitting materials.

摘要 i
ABSTRACT ii
誌謝 iv
目錄 v
表目錄 vii
圖目錄 viii
縮寫對照表 xii
第一章 緒論 1
1-1前言 1
1-2文獻回顧 2
1-2-1 2-苯基吡啶 2
1-2-2 糖精 3
1-2-3 吡啶與糖精之鹽類 3
1-2-4 有機電激發光原理 4
1-2-5 三原色磷光材料之發展 5
1-2-5-1 綠色磷光材料 5
1-2-5-2 藍色磷光材料 6
1-2-5-3 紅色磷光材料 6
1-2-6螢光及磷光理論 7
1-3 研究動機 9
第二章 實驗方法 10
2-1 藥品材料 10
2-2 儀器 12
2-3 實驗部分 16
2-3-1 合成金屬錯合物ppy-Rf-AuCl3 16
2-3-2 合成金屬錯合物ppy-Rf-AuCl2 17
2-3-3 合成氟鏈糖精鹽 18
2-4 含短氟鏈短氟鏈2-苯基吡啶配位基之金金屬錯合物與糖精鹽之鑑定數據 19
第三章 結果與討論 39
3-1 含氟鏈金錯合物之鑑定 39
3-1-1 NMR 39
3-1-2 FT-IR 41
3-2 含短氟鏈2-苯基吡啶糖精鹽之鑑定 42
3-3理論計算 43
3-3-1 ppy-Rf-AuCl2理論值與實驗值對比 43
3-3-2 ppy-Rf-Saccharinate理論值與實驗值對比 48
3-4晶體結構探討 49
3-5 螢光性質之探討 53
第四章 結論 55
參考文獻 56
圖譜 59
附錄 94

1. 李紫瑄，短氟鏈2-苯基吡啶及其銥金屬錯合物之合成與光物理性質探討，碩士論文，國立台北科技大學有機高分子所，台北，2018.
2. 江幸芳，(b)含氟化合物作為提供者或接受者之非共價鍵結探討，碩士論文，國立台北科技大學有機高分子所，台北，2017.
3. Zhou, G.; Wong, W. Y.; Yang, X., New design tactics in OLEDs using functionalized 2-phenylpyridine-type cyclometalates of iridium(III) and platinum(II). Chem Asian J 2011, 6 (7), 1706-27.
4. Janzen, D. E.; Doherty, S. R.; VanDerveer, D. G.; Hinkle, L. M.; Benefield, D. A.; Vashi, H. M.; Grant, G. J., Cyclometallated gold(III) complexes with a trithiacrown ligand: Solventless Au(III) cyclometallation, intramolecular gold–sulfur interactions, and fluxional behavior in 1,4,7-trithiacyclononane Au(III) complexes. Journal of Organometallic Chemistry 2014, 755, 47-57.
5. Garg, J. A.; Blacque, O.; Venkatesan, K., Syntheses and photophysical properties of luminescent mono-cyclometalated gold(III) cis-dialkynyl complexes. Inorg Chem 2011, 50 (12), 5430-41.
6. Lu, N.; Tu, W.-H.; Hou, H.-C.; Lin, C.-T.; Li, C.-K.; Liu, L.-K., Synthesis, structure and spectroelectrochemical property of (2,2′-bipyridine)–metal (M=Pt, Pd) dichloride with 4,4′-bis(fluorous-ponytail) on bipyridine. Polyhedron 2010, 29 (3), 1123-1129.
7. Lu, N.; Tu, W.-H.; Shing, J.-S.; Wen, Y.-S.; Liu, L.-K., New type of saccharinate crystals: A possible supramolecular synthon. Journal of Molecular Structure 2010, 980 (1-3), 101-107.
8. Lu, N.; Chang, W.-H.; Wei, R.-J.; Fang, Y.-C.; Han, T.-W.; Wang, G.-Q.; Chang, J.-Y.; Wen, Y.-S.; Liu, L.-K., Pyridinium saccharinate salts as efficient recyclable acylation catalyst: a new bridge between heterogeneous and homogeneous catalysis. Tetrahedron 2016, 72 (24), 3468-3476.
9. Banerjee, R.; Bhatt, P. M.; Ravindra, N. V.; Desiraju, G. R., Saccharin Salts of Active Pharmaceutical Ingredients, Their Crystal Structures, and Increased Water Solubilities. Crystal Growth & Design 2005, 5 (6), 2299-2309.
10. Bhatt, P. M.; Ravindra, N. V.; Banerjee, R.; Desiraju, G. R., Saccharin as a salt former. Enhanced solubilities of saccharinates of active pharmaceutical ingredients. Chem Commun (Camb) 2005, (8), 1073-5
11. Chattoraj, S.; Shi, L.; Chen, M.; Alhalaweh, A.; Velaga, S.; Sun, C. C., Origin of Deteriorated Crystal Plasticity and Compaction Properties of a 1:1 Cocrystal between Piroxicam and Saccharin. Crystal Growth & Design 2014, 14 (8), 3864-3874.
12. Chadha, R.; Saini, A.; Jain, D. S.; Venugopalan, P., Preparation and Solid-State Characterization of Three Novel Multicomponent Solid Forms of Oxcarbazepine: Improvement in Solubility through Saccharin Cocrystal. Crystal Growth & Design 2012, 12 (8), 4211-4224.
13. Aitipamula, S.; Chow, P. S.; Tan, R. B. H., Dimorphs of a 1 : 1 cocrystal of ethenzamide and saccharin: solid-state grinding methods result in metastable polymorph. CrystEngComm 2009, 11 (5)
14. Finkenzeller, W. J.; Yersin, H., Emission of Ir(ppy)3. Temperature dependence, decay dynamics, and magnetic field properties. Chemical Physics Letters 2003, 377 (3-4), 299-305.
15. Fereidoonnezhad, M.; Kaboudin, B.; Mirzaee, T.; Babadi Aghakhanpour, R.; Golbon Haghighi, M.; Faghih, Z.; Faghih, Z.; Ahmadipour, Z.; Notash, B.; Shahsavari, H. R., Cyclometalated Platinum(II) Complexes Bearing Bidentate O,O′-Di(alkyl)dithiophosphate Ligands: Photoluminescence and Cytotoxic Properties. Organometallics 2017, 36 (9), 1707-1717.
16. Bronner, C.; Wenger, O. S., Luminescent cyclometalated gold(III) complexes. Dalton Trans 2011, 40 (46), 12409-20.
17. Fernandez-Cestau, J.; Bertrand, B.; Blaya, M.; Jones, G. A.; Penfold, T. J.; Bochmann, M., Synthesis and luminescence modulation of pyrazine-based gold(III) pincer complexes. Chem Commun (Camb) 2015, 51 (93), 16629-32.
18. Wong, B. Y.; Wong, H. L.; Wong, Y. C.; Au, V. K.; Chan, M. Y.; Yam, V. W., Multi-functional bis(alkynyl)gold(iii) Ninsertion markC complexes with distinct mechanochromic luminescence and electroluminescence properties. Chem Sci 2017, 8 (10), 6936-6946.
19. Crespo, O.; Gimeno, M. C.; Laguna, A.; Montanel-Pérez, S.; Villacampa, M. D., Facile Synthesis of Gold(III) Aryl–Carbene Metallacycles. Organometallics 2012, 31 (15), 5520-5526.
20. Bojan, V. R.; López-de-Luzuriaga, J. M.; Manso, E.; Monge, M.; Olmos, M. E., Metal-Induced Phosphorescence in (Pentafluorophenyl)gold(III) Complexes. Organometallics 2011, 30 (17), 4486-4489.
21. Fernandez-Cestau, J.; Bertrand, B. t.; Pintus, A.; Bochmann, M., Synthesis, Structures, and Properties of Luminescent (C∧N∧C)gold(III) Alkyl Complexes: Correlation between Photoemission Energies and C–H Acidity. Organometallics 2017, 36 (17), 3304-3312.
22. Saitoh, M.; Balch, A. L.; Yuasa, J.; Kawai, T., Effects of counter anions on intense photoluminescence of 1-D chain gold(I) complexes. Inorg Chem 2010, 49 (15), 7129-34.