含三吡啶二價金屬(鋅/釕)之新型金屬錯合高分子之合成與應用

Abstract

本論文研究方向為探討一系列包含三吡啶(Terpyridine)二價金屬(鋅/釕) (Zinc(II)/Ruthenium(II))之錯合高分子之合成與其在光電材料的應用，並以三大方向為研究主軸。第一個部份，以炔基(ethylene)連接的茀(Flourene)單元為高分子的主鏈結構，並包含(Carbazole)或圻堮雙唑(oxadiazole)懸掛物之新型金屬錯合高分子。第二，將具有不同官能基(Me, OMe, F)的苯環單元加入至此系列金屬高分子中，並一樣藉由炔基與中心的茀以共軛的方式與其連接。最後一部份，以改變高分子中心主鏈結構(Phenothiazine)及錯合物之金屬部分做為研究的主題。在鑑定方面，藉由1H NMR光譜圖上的積分值可輕易的鑑定出金屬錯合高分子的主鏈結構是由不同的單體而建構(例：金屬錯合單一相高分子和金屬錯合共聚高分子)。然而，利用紫外光-可見光和螢光光譜儀，藉由改變金屬二價鋅離子的濃度，做滴定實驗亦可進一步的証明金屬錯合高分子的結構。結果發現，藉由金屬錯合的方式所形成的高分子，可提高熱穩定性(熱烈解溫度)及量子產率。以比較此系列高分子的量子產率為例，加入OXD可有效的提高量子產率而CAZ則否。再者，探討以此具有發光性質的金屬錯合高分子作為發光層並應用於電激發光元件，發現加入具有電子傳出能力的OXD與電洞傳出能力的CAZ懸掛物的高分子上，具有提高元件效率的結果。最後，將此類型高分子以二價釕離子取代原本的鋅離子，探討其與原本以鋅為錯合金屬離子之物理及化學性質的差別，並將其應用於太陽能電池元件上。

A series of novel terpyridyl-zinc(II) based metallo-polymers containing carbazole (CAZ) or 1,3,4-oxadiazole (OXD) pendants (attached to the C-9 position of fluorene by long alkyl spacers) were synthesized by self-assembling reactions. On the other hand, the phenylene units with various lateral substituents (Me, OMe, F) were added to such metallo-polymeric backbones structures and conjugated with central fluorene units by ethylene bridges. The integrated ratios of 1H NMR spectra reveal a facile result to distinguish the well-defined main-chain metallo-polymeric structures (i.e. metallo-homopolymers and copolymers) which were constructed by different monomer ligand systems. Furthermore, UV-visible and photoluminescence (PL) spectral titration experiments were carried out to verify the metallo-polymeric structures by varying the molar ratios of zinc(II) ions to monomers. As a result, the enhancement of thermal stability (Td) and quantum yields were introduced by the metallo-polymerization, and their physical properties were mainly affected by the nature of the pendants. For example, in contrast to metallo-polymers containing alkyl pendants, the quantum yields were greatly enhanced by introducing OXD pendants but reduced by CAZ pendants. The electroluminescent (EL) devices with these light-emitting metallo-polymers as emitters have been investigated and EL performance were enhanced by incorporating with electron-transporting OXD and hole-transporting CAZ pedants. Finally, metallo-polymers were produced by coordination of Ruthenium(II) metal ions with two ditopic terpyridyl (tpy) receptor monomers containing central fluorene and phenothiazine units, respectively. Such polymers blended with fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) and fabricated into photovoltaic cells (PPVCs).