臺灣博碩士論文加值系統

本篇論文是以萘環為結構中心，選擇在具有立體障礙的1,8位置(Peri)分別接上一個咔唑基團以及不同拉電子基團(噁二唑、苯并咪唑、丁腈、硝基、甲酸基)，合成一系列可藉由立體障礙阻斷共軛的雙偶極咔唑化合物。由於推拉電子基團之間的距離十分接近，所以針對不同拉電子基的化合物進行光物理及電化學性質的測量與比較，並觀察基團間可能的交互作用。另外，將咔唑基團置換成具有重原子效應的溴原子，對這些不同拉電子基的萘溴衍生物進行光物理及電化學性質的比較與探討。
經由螢光、磷光光譜以及循環伏安法的測量結果，得知所有萘化合物的最低未填滿分子軌域(LUMO)及三重激發態都是位在萘環結構上，而且三重激發態的能階並不會隨著取代基改變而有太大的變化，其中雙偶極萘化合物皆在2.55 eV附近，以化合物12為代表與綠光磷光有機發光二極體(PhOLED)之客發光體Ir(ppy)3以及紅光磷光有機發光二極體之客發光體Ir(2-phq)2(acac)進行能量轉移實驗，得知其對於Ir(ppy)3與Ir(2-phq)2(acac)良好的能量轉移效率，未來也許有作為綠光及紅光有機發光二極體主發光體材料的潛力。

In this study, a series of bipolar compounds that containing carbazole group at the 8-position of naphthalene, and with the 1-position substituted by an electron-withdrawing group (oxadiazole, benzimidazole, nitrile, and nitro, formic acid) were synthesized. The 1,8-position di-substituted naphthalene, being called as peri-substituted of naphthalene derivatives, has large steric hindrance resulting an orthogonal arrangement that interrupted the conjugation between the donating and the withdrawing groups. The 8-position substituted carbazole of naphthalene derivatives were discussed that intermolecular interaction between carbazole and withdrawing moieties and through measuring photophysical and electrochemical properties. Furthermore, we replaced carbazole group with bromine which has heavy atom effect, and demonstrated the properties of these naphthalene derivatives with different withdrawing moieties through measuring photophysical and electrochemical properties.
Fluorescence, phosphorescence spectra and cyclic voltammetry were used to characterize the 1, 8-position di-substituted of naphthalene. The LUMO and the triplet state of all naphthalene derivatives are located in naphthalene structure. The triplet energy doesn’t change a lot with different substituent. The triplet energy of bipolar naphthalene derivatives are about 2.55 eV, and we found that compound 12 can transfer energy to the Ir(ppy)3 and the Ir(2-phq)2(acac) efficiently, so it is possible that these bipolar naphthalene derivatives become a good host material of green and red PhOLED.

摘要 I
Abstract II
目錄 IV
表目錄 VI
圖目錄 VIII
流程目錄 XIII
附錄目錄 XIV
化合物結構與編號 XVII
第一章 緒論 1
1.1前言 1
1.2有機分子電子躍遷形式6,7 2
1.3有機分子發光原理7,8,9 4
1.4螢光與分子結構7 7
1.5溶劑效應(Solvent effect)12 9
1.6 π-π交互作用(π-π interaction)13 10
第二章 文獻回顧 11
2.1 Peri位向取代萘環的相關文獻回顧 11
2.2研究動機與分子設計 24
第三章 結果與討論 30
3.1合成策略及方法 30
3.1.1噁二唑之咔唑化合物7、溴化合物6、對比物9之合成步驟 31
3.1.2苯并咪唑之咔唑化合物12、溴化合物11、對比物13之合成步驟 34
3.1.3丁腈之咔唑化合物16、溴化合物15、對比物n-CN之合成步驟 36
3.1.4硝基之咔唑化合物18、溴化合物17、對比物n-NO2之合成步驟 38
3.1.5羧酸基之咔唑化合物20、溴化合物3、對比物n-COOH之合成步驟 40
3.1.6 H之咔唑化合物21、溴化合物n-Br、對比物n之合成步驟 42
3.1.7三氮唑之咔唑化合物28 (失敗)、溴化合物25、對比物26之部分合成步驟 43
3.1.8 1號位置取代基為萘環之咔唑化合物30(失敗)、溴化合物29、對比物n-n之部分合成步驟 46
3.2 X-ray晶體結構解析 48
3.3光學性質分析 76
3.3.1光物理性質分析 76
3.3.2薄膜光物理性質分析 92
3.3.3固態粉末光物理性質分析 94
3.4電化學性質分析 96
3.5熱性質分析 114
3.6能量轉移實驗 118
第四章 結論 123
第五章 實驗部分 125
5.1實驗儀器與試劑 125
5.1.1儀器部分 125
5.1.2試劑與溶劑 126
5.2合成步驟 127
第六章 參考文獻 157
附錄 166
附錄一　化合物的X – ray晶體參數表、鍵長與鍵角資料 166
附錄二　化合物的氫核磁共振光譜及碳核磁共振光譜 223

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