高分子電致發光材料之合成與性質研究

Abstract

本論文分為兩個部份。第一部份，我們以Claisen 縮合反應合成新的β-diketone衍生物，此β-diketone同時具備高分子聚合反應官能基及雙螯合金屬配位基的功能，藉由修飾C^N金屬配位基，順利合成出紅光BTPBr、綠光PPYBr及天空藍DFPBr之銥金屬磷光錯合物聚合單體，可作為一客體磷光掺雜材料，適用於Suzuki聚合反應，鑲嵌於各類主體發光材料高分子主鏈，得到一系列新型之磷光高分子發光材料，可藉由主體與客體材料之能量轉移機制提昇發光效率，並且使用旋轉塗佈成膜方式大幅簡化電致發光元件之製程。 論文之第二部份將探討一系列掌性噻吩共聚高分子之化學合成、物理性質及結構特徵。以天然L(+)與非天然D(-)酒石酸為起始物建構出兩個具有雙掌性中心之共環噻吩衍生物聚合單體，再以Suzuki聚合反應分別與兩種共軛發光材料聚合單體共聚合，可得到掌性噻吩共聚高分子P1、P2。經由高分子在不同溫度之多種溶劑系統與薄膜態的光物理與光學性質分析，藉此了解高分子之分子內與分子間交互作用，試比較高分子與寡聚分子，可以推測高分子主鏈之螺旋構形。此一系列掌性高分子與寡聚分子具備光電應用材料之潛力，可作為一不對稱放光源或液晶旋光劑。

This thesis is divided into two parts, in the first part, β-diketone equipped with functional sites for Suzuki coupling polymerization has been synthesized via Claisen condensation. The designated functionalized diketone was chelated to iridium (III) center bearing with different cyclometalated ligands to form phosphorescence-emitting red-BTPBr, green-PPYBr, and sky blue-DFPBr complexes. These complexes were used as guest-monomer covalently attached to common fluorescent host-monomers to generate new light-emitting polymeric materials via Suzuki polymerization. These phosphorescent polymers exhibited improved efficiency in host-guest energy transfer, which could be potentially used to simplify device fabrication processes. The second part of this thesis deals with the synthesis, physical properties and characterizations of structural features of new thiophene-embedded chiral polymers. Thiophene fused to a carbocycle bearing with two chirality centers originated from natural L(+) and unnatural D(-) tartaric acids was synthesized to be the chiral monomers which was coupled with two conjugated monomers, respectively, via Suzuki coupling polymerization to give novel chiral polymers. Investigations on the photophysical and optical properties of these polymers in various solvent systems as well as solid thin films with different temperature variations were conducted to probe the intra- and inter-chain interactions. By comparison to those of their low molecular weight counterparts, helical structures formed within the polymeric chain were proposed. These oligomers and copolymers may be served as potential candidates to optoelectronic applications such as polarized light source or chiral dopant in liquid crystal displays.