摘要
本論文以Heck反應合成PTP-SiO及PTP-P-SiO兩系統之高分子，此兩高分子主鏈上含有交替出現之含氮雜環及柔軟矽氧連結基團具良好之熱穩定性及加工性。在光學性質方面，兩高分子系統可放射出藍綠之可見光(491~520 nm)。
根據Pearson的軟-硬酸-鹼理論(Hard-Soft Acid-Base, HSAB)，有機化合物之氮及氧等原子可與過渡金屬離子或稀土金屬離子複合而形成有機-無機錯合物，因此可藉由兩高分子系統中的含氮雜環與不同金屬離子形成的錯合物，並加以探討其吸收和發光性質。在吸收光譜中，錯合物的π-π*及n-π*電子躍遷分別出現於在275~290 nm及320~330 nm吸收帶。而在發射光譜中，錯合物的π-π*及n-π*電子躍遷分別出現於408~420 nm及491~520 nm 發射帶。綜合所有光學性質，含-N=N-雜環的高分子，其吸收及發射光譜變化較含吡啶雜環之高分子更為明顯。這些變化可進一步使用在化學偵測器上，來偵測金屬離子之含量。

Abstract
Two novel conjugated polymers (PTP-SiO) and (PTP-P-SiO) with alternating N-containing heterocycles and siloxane (-Si-O-) units were synthesized using the Heck reaction. The incorporation of siloxane units in the polymers improves their thermal stability and processability. The polymers can be dissolved in organic solvent and exhibited good thermal stability with 5％ weight loss temperature above 370℃ under nitrogen atmosphere. The photoluminescence (PL) spectra of PTP-SiO and PTP-P-SiO in solution show maximum peaks at 491 and 520 nm respectively. The heterocycles in the two polymers contain N- atoms, which can coordinate with transition or lanthanides metal ions to form complexes. The absorption spectra show peaks at around 275~290 nm and 320~330 nm, which are attributed to π-π* and n-π* transitions, respectively. On the other hand, the emission spectra consist of peaks at around 408~420 nm and 491~520 nm. These two emission peaks belong to π-π* and n-π* transitions of the ligands, respectively. With pyridazine ( heterocycle with –N=N- group) ring, PTP-P-SiO shows more significant variation upon coordination with metals ions as compared to PTP-SiO. These variations of optical property offer a possibility for application in chemosensors for detection of metal ions.

目錄

摘要 i
英文摘要 ii
目錄 iii
流程目錄 v
表目錄 vi
圖目錄 vii

第一章 緒論 1
§1.1 高分子發光二極體之發展 4
§1.2 共軛高分子的金屬錯合物 8

第二章 未來研究方向與文獻回顧之啟發 9
§2.1 雜環化合物的合成方法 9
§2.2 共軛發光高分子之聚合方法 10
§2.3 雜環高分子和金屬錯合物的文獻回顧 14
§2.4 金屬離子間電子轉移的機制 21
§2.5 金屬與金屬間電荷的轉移之研究 21
§2.6 高分子化學結構對金屬離子錯合之影響 22
§2.7 研究動機 23

第三章 實驗部分 24
§3.1 實驗裝置及設備 24
§3.2 分析儀器 24
§3.3 藥品 26
§3.4 實驗部分 28
第四章 結果與討論 34
§4.1 前言 34
§4.2 單體的合成及結構鑑定 34
§4.3 高分子的聚合及結構鑑定 36
§4.4 化合物的熱性質分析 36
§4.5 化合物的溶解度測試 38
§4.6 化合物的光學性質分析 38

第五章 結論 45

參考文獻 89

參考文獻

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