結合密度泛函理論 (DFT) 及光譜量測探討二、三列過渡金屬錯合物之光物理特性及質子/電子轉移之光化學反應

The combination of theoretical and experimental approaches to study the emissive properties of second- and third-row transition metal complexes and the photochemistry of excited-state proton/charge transfer reaction

鍾敏玟(Min-Wen Chung)

指導教授 ： 周必泰

國立臺灣大學/理學院/化學研究所/碩士(2010年)

https://doi.org/10.6342/NTU.2010.10252

摘要

以過渡金屬錯合物為發光主體的有機發光二極體(OLED)，有極大的潛力能夠取代傳統燈泡做為下一代主要的照明設備及平面顯示器。但目前所開發出來主要做為OLED元件中發光層的客體材料仍然有許多的缺點尚待克服。例如：發光效率不佳、壽命不長…等缺點。除此之外，能夠涵蓋所有可見光範圍的白光元件以及藍光的放光材料更是需要透過更好的分子設計，才能再做更進一步的改善。因此，本篇論文的第一部分就一系列銥、釕、鋨等有機金屬錯合物做詳盡的光譜分析及理論計算，探討其在激發態的光物理特性，希望能夠透過這深入的了解，提供往後在分子設計上有新的想法做更進一步的突破。
本篇論文的第二部分，則是對一系列的quinoline/isoquinoline-pyrazole/pyrrole 結構異構物或衍伸物進行詳盡的光譜量測及理論計算。探討其在激發態時的質子轉移及動力學研究。我們發現,簡單利用一些不同的結構異構物(有著不同的共振結構)，對於它們在激發態進行質子轉移的驅動力會有很大的不同。除此之外，控制這些分子的異曲性(flexibility)，甚至能夠去轉換它們進行質子轉移的型態(ESIPT/ESDPT)。藉由這一系列有系統的探討，對於往後在質子轉移研究的分子設計，或未來應用在感測等部分，會有很大的幫助。

關鍵字

光譜 ； 有機發光二極體 ； 理論計算 ； 質子轉移反應

並列摘要

The emissive layer of OLED device based on the transition metal complexes has a great potential to be the major role in light and display on the commercial market in the future. However, there are still many drawbacks in the current devices, such as bad efficiency and short emissive lifetime. In addition, the white light OLED device which can cover the whole visible wavelength range and the true-blue emissive materials still need to be improved based on advanced molecular design. Therefore, the first part of this thesis is using both theoretical and experimental approaches to study the photophysical properties of a series of second- and third-row transition metal complexes. We hope that we can get new ideas to make a breakthrough in molecular designs by such a comprehensive study.
The second part of this thesis focuses on a series of quinoline/isoquinoline-pyrazole/pyrrole isomers or derivatives. We apply comprehensive theoretical and spectroscopic approaches to study excited-state proton transfer (ESPT) and the kinetic process. We have found that the driving force for ESIPT process can be fine tuned by just changing the resonance structure of the derivatives/isomers. In addition, the proton transfer type can even be switched from ESIPT to ESDPT by controlling the geometrical flexibility. Such a structure-versus-proton transfer relationship is of fundamental importance and can be exploited in strategic design of proton-transfer systems, facilitating their applications in several urgent fields.

並列關鍵字

spectroscopy ； OLEDs ； DFT ； proton transfer

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