(1) 含2-吡啶吡唑族配基之有機鋨異構錯合物之光致發光性質比較 (2) 鄰位綠螢光蛋白質發光團：七元環氫鍵系統中的激發態分子內質子轉移

Abstract

本篇論文分成兩大部分。第一部分為有機發光二極體（OLED）之發光染料分子的光物理化學研究。第二部分則為鄰位綠螢光蛋白（GFP）發光團分子的分子內質子轉移現象的探討。 有機發光二極體之發光染料分子的光物理化學研究在這幾年來一直是我們實驗室的研究重心。藉由與清大季昀教授團隊的合作，我們發表了一系列以第二、第三列過渡金屬（如釕、鋨、銥等）為中心的金屬錯合物的研究論文，藉由改變配位基（通常是2-吡啶吡唑族配位基之衍伸物）上取代基團的推拉電子能力來影響金屬錯合物的電子躍遷型態與能階，因此可以得到發光範圍從藍光到紅光的一系列分子。 本篇論文第一章，即在介紹這一系列過渡有機金屬錯合物的分子結的設計策略，以及其相對應之光物理化學性質之研究。第二章則針對一對含2-吡啶吡唑族配位基之有機鋨異構錯合物，探討兩個異構物間因為配基位置的不同而有相異的電子躍遷型態，因此有截然不同的光物理性質。 綠螢光蛋白被廣泛應用在細胞生物學和分子生物學中作為報導基因。利用合成方法我們合成出鄰位的綠螢光蛋白之發光團分子，並發現其具有激發態分子內質子轉移的現象。第三章簡介了激發態分子內質子轉移在數十年來的進展；第四章則介紹近期我們實驗室的研究，探討鄰位的綠螢光蛋白之發光團分子的光物理性質，同時我們也合成出一系列的衍伸物，得到從580-670 nm 的發光波長。

part 1. A general review of 2nd and 3rd – row transition-metal complexes incorporating chelating chromophores, which serves as phosphorescent dyes for organic light-emitting diodes, will be depicted in chapter 1. Group of Chi have synthesized two monometallic and isomeric complexes 3 and 4 with the coordination of two phosphine ligands located in the trans-disposition and one CO and one hydride located opposite to the pyridyl triazolate chelate. Chapter 2 focuses on subtle differences in photophysical properties examined for isomers 3 and 4 on the basis of steady state absorption and emission, the relaxation dynamics, and temperature- dependent luminescent studies. The results, in combination with time-dependent density function theory (TDDFT) calculations, provide fundamental insights into the future design and preparation of highly efficient phosphorescent emitters. part 2. In chapter 3 the focus is mainly limited to the subject related to the photoinduced excited-state inter/intra-molecular proton transfer (ESPT) process, forming a proton-transfer isomer. Our main goal aims at bi-functional molecules possessing a proton donor group and a proton acceptor group so that ESPT takes place either intramolecularly (i.e. intrinsically) or through the assistance of the guest molecules. Futhermore, a structural isomer of the core chromophore (p-HBDI) in green fluorescence protein, o-HBDI, and as well as a new series of ortho-hydroxy analogues, is synthesized. o-HBDI possesses a seven-membered-ring hydrogen bond, from which the excited-state intramolecular proton transfer takes place, resulting in a remarkable tautomer emission of ~605 nm and be fully discussed in chapter 4.