1,3,2-苯并二氮雜硼引入三咔唑及關環之苯并咪唑之合成、性質探討及其在藍色磷光有機發光二極體及陰離子偵測之應用

Synthesis and Characterization of 1,3,2-Benzodiazaboroles Substituted Tricarbazole and Benzo[4,5]imidazo[1,2-f]phenanthridine and Their Applications in Blue PhOLEDs and Anion Detection

王卉欣(Huei-Sin Wang)

指導教授 ： 梁文傑

國立臺灣大學/理學院/化學研究所/碩士(2019年)

https://doi.org/10.6342/NTU201901096

摘要

以往有機發光二極體的材料中，多半僅具有碳氮兩種原子，我們藉由等電子體之概念，將吲哚結構中的碳─碳雙鍵取代為硼─氮單鍵，使得硼原子得以引入有機發光二極體材料中，因而合成出一系列以1,3,2-苯並二氮雜硼作為主體之有機材料。
這一系列1,3,2-苯並二氮雜硼之材料具有10個π電子及硼的空pz軌域之特色，使其表現出獨樹一格的電致發光性質，且因硼的電負度較碳及氮的電負度低，也期望能使有機材料之最低未占分子軌域( LUMO )有所提升，並藉由提升分子量、分子結構變得剛硬兩種方法，使得有機發光二極體材料在玻璃轉換溫度上有大幅的提升，並以m3Cb作為電子阻擋層應用於有機發光二極體元件上，元件表現如下，驅動電壓為8.14 V，最大亮度為9280 cd/m2，光色比mCP元件偏向藍光，元件最大的電流效率為38.87 cd/A，最大功率效率為23.9 lm/W，外部量子效率為18.59%，且在施以高電壓時以m3Cb作為電子阻擋層元件的頻譜依舊偏藍。
而在陰離子偵測的部分，我們則發現溶液中有多種離子會與以1,3,2-苯並二氮雜硼為主體之材料產生反應。其中以氟離子( F- )最為顯著，加入氟離子後會導致化合物的常溫螢光放射光譜有立即被淬息之狀況；加入氫氧根離子( OH- )後之趨勢與氟離子相似。除此之外，在加入磷酸二氫根離子( H2PO4- )、焦磷酸二氫根( H2P2O72- )後，則是發現化合物的常溫螢光放射光譜會隨著時間有紅移之狀況。以目前的實驗結果，以1,3,2-苯並二氮雜硼為主體之材料有望作為偵測多重離子的一種化學感測器。

關鍵字

硼氮吲哚 ； 有機含硼化合物 ； 1,3,2-苯並二氮雜硼 ； 陰離子偵測 ； 有機發光二極體

並列摘要

In the past, the materials of organic light emitting diodes only had carbon and nitrogen atoms, so we replace C=C to B-N in indoles by using the concept of isostere, letting organoboron compounds appeared in the materials of organic light emitting diodes, then synthesize a series of 1,3,2-benzodiazaborole derivatives.
This series of 1,3,2-benzodiazaborole derivatives has 10πeletron and empty pz orbital, leading to its special electroluminescence properties. Having boron atoms, let the LUMO of these compounds get higher. Moreover, we enhance Tg of these series of 1,3,2-benzodiazaborole derivatives by increasing the molecular weight and making the structure rigid in order to stablize the film using in organic light emitting diodes.
Besides, the anion detection experiments show that many kinds of anions in the solutions can let the photophysical properties of compounds change. In the case of fluoride ion, adding the fluoride ion to the soluton of compounds leads to fluorescence quenching immediately. In the case of hydroxide ion, the result is as same as fluoride ion. However, in terms of dihydrogen phosphate and dihydrogen pyrophosphate, we discover that fluorescence of the compound will red-shift along with time. Up to now, we think that 1,3,2-benzodiazaborole derivatives can detect multi-anion, and it has potential to become chemosensor.

並列關鍵字

B-N indole ； organoboron ； 1,3,2-benzodiazaborole ； anion detection ； OLED

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