(一)具聚集誘導發光特性與苯並咪唑－咔唑骨架之刺激－響應開啟螢光探針 (二)含氰基之紅－近紅外光發光之有機材料合成

(1)A Combination of Benzimidazole-Carbazole Backbone with AIE Luminophores as Turn-On Fluorescent Probes (2)Synthesis of Cyano-Based Red-NIR Light‐Emitting Organic Materials

林郁庭(Yu-Ting Lin)

指導教授 ： 梁文傑

國立臺灣大學/理學院/化學研究所/碩士(2022年)

https://doi.org/10.6342/NTU202204113

摘要

本論文主要分為兩個部分，第一部分為具聚集誘導發光特性與苯並咪唑－咔唑骨架之高靈敏度及高選擇性的刺激－響應開啟螢光探針；第二部分為含氰基之紅－近紅外光發光之有機材料合成。
第一部分為延續本實驗室林珮琪學姊的研究，將本實驗室所合成具聚集誘導發光特性之 o-BzcDPE 與 p-BzcDPE 應用於強酸檢測探針上。此兩分子以 1,1-二苯基乙烯作為聚集誘導放光主體，並引入苯并咪唑－咔唑骨架，在中性環境下，此分子於固體及溶液態下皆為微弱之紫色螢光，而在酸性環境下，兩探針皆表現出明顯對比之綠色螢光開啟機制，不僅適用於肉眼檢測，且具有選擇性高、靈敏度高、反應時間短、良好的光穩定性等優點，能夠對強酸進行定量檢測並具有良好的線性關係。透過X-ray 單晶繞射分析、NMR 光譜以及理論計算可以進一步對螢光響應機制進行探討，證實為其苯并咪唑之質子化增加其拉電子效果並且增強分子內電荷轉移 (Intramolecular charge transfer, ICT)，使 1,1-二苯基乙烯基的螢光猝滅效應降低，綠色螢光的量子產率提高。
在應用上，對強酸之肉眼偵測及定量檢測上皆有不錯的表現，此外，此螢光分子可製備為可攜帶式試紙，可對水溶液中的質子進行偵測，不受金屬陽離子的干擾，偵測結果亦可用於酸雨判斷之標準，且此試紙具有再生性。各偵測結果皆可看出此兩螢光探針於不同領域的應用開發上具不錯的發展性及利用價值。
第二部分研究目標為於紅光 TADF 材料中之電子受體引入氰基，增加其電子受體拉電子能力效果，使其可以達到減小 ΔEST，並且放光紅移。經核磁共振光譜儀及質譜儀可以確認成功合成出 pTPADPPZdCN，經過與 pTPA-DPPZ 進行比較後，發現具有雙氰基之 pTPADPPZdCN 的螢光放射波長可以有效紅移至 719 nm，且具有一足夠小的 ΔEST，初步推測其具有 TADF 的性質。待後續對其分子的性質分析研究探討，並且也期望可以合成出一系列含氰基之 TADF 材料，期許於有機發光二極體元件上能有不錯的應用。

關鍵字

1,1-二苯基乙烯 ； 咔唑 ； 苯并咪唑 ； 質子偵測 ； 螢光探針 ； 聚集誘導放光 ； 有機發光二極體 ； 紅光 ； 近紅外光 ； 氰基 ； 熱活化延遲螢光

並列摘要

In section one, two aggregation-induced emission luminogens (AIEgens) with the incorporation of benzimidazole-carbazole backbone, o-BzcDPE and p-BzcDPE, have been synthesized by Pei-Chi Lin. Both probes showed evident turn-on green fluorescence from the nearultraviolet region upon the addition of trace strong acid. These probes have high selectivity, excellent sensitivity, short response time, great photo-stability and are capable of quantitative detection with a good linear relationship. Moreover, by using the 1H NMR analysis, X-ray crystallographic analysis and the DFT calculations, we verified that the protonation of the C = N unit in the benzimidazole moiety increased the electron-withdrawing ability of benzimidazole and enhanced the intramolecular charge transfer (ICT) effect, which was the primary reason accounted for the turn-on fluorescence phenomenon.
In application, it has good performance in visual detection and quantitative detection of strong acid. In addition, this fluorescent molecule can be prepared as a portable test paper, which can detect protons in aqueous solutions system without the interference of metal cations. The detection results can also be used for the acid rain identification, and this test paper is recyclable. Finally, these two probes were systematically investigated and had great potential for practical application.
In section two, pTPADPPZdCN has been designed and successfully synthesized. It is also expected that introducing cyano groups with stronger electron-drawing ability into the electron acceptor in red TADF material can reduce ΔEST and the fluorescence emission will red shift. After comparing with pTPA-DPPZ, it is found that the fluorescence emission of pTPADPPZdCN can be effectively red-shifted to 719 nm, and has a small ΔEST, which preliminarily speculates that it has the properties of TADF.The properties of pTPADPPZdCN will be analyzed and discussed in the future. It is also expected that a series of cyano group-containing TADF materials can be synthesized, which is expected to be used in organic light-emitting diode with nice performance.

並列關鍵字

1,1-diphenylethylene ； carbazole ； benzimidazole ； proton detection ； fluorescent sensor ； aggregation induced emission effect ； organic light-emitting diode ； Red-NIR ； cyano group ； thermally activated delayed fluorescence

參考文獻

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