【摘要】：金屬配合物固體熒光材料已廣泛應(yīng)用于染料激光器、有機發(fā)光二極管(OLED)、數(shù)據(jù)記錄和存儲、以及安全印刷等多種新興的領(lǐng)域。隨著科學的發(fā)展和社會的進步,一些具有刺激響應(yīng)型金屬配合物固體熒光材料已廣泛應(yīng)用于染料激光器、有機發(fā)光二極管(OLED)、數(shù)據(jù)記錄和存儲、以及安全印刷等多種新興的領(lǐng)域。隨著科學的發(fā)展和社會的進步,一些具有刺激響應(yīng)型的金屬配合物固體熒光材料已然成為人們關(guān)注的焦點。這類材料通過改變一些條件,如機械研磨(力致變色)、熱處理(熱致變色)、光處理(光致變色)、通電(電致變色)和通過蒸氣熏蒸(氣致變色)可以響應(yīng)外部刺激從而表現(xiàn)出不同的光性質(zhì)。此類敏感材料在信息記錄、數(shù)據(jù)存儲、防偽商標和光電器件等方面有著重要的現(xiàn)實意義和廣泛的應(yīng)用前景。萘酰亞胺類希夫堿、苯并咪唑和苯并惡唑類衍生物由于具有良好的配位能力和結(jié)構(gòu)的多樣性,也成為人們關(guān)注的焦點。以這些衍生物合成的配合物不僅結(jié)構(gòu)易于修飾,配位模式多樣,而且具有良好的發(fā)光性能。基于上述研究背景,本論文以萘酰亞胺類希夫堿、苯并咪唑基吡啶和苯并惡唑基吡啶為配體,設(shè)計合成了一系列新型配合物,采用紅外光譜、核磁共振氫譜、X-射線單晶衍射等方法進行了表征,并對這些配合物的固態(tài)熒光性質(zhì)和熱穩(wěn)定性進行了研究。具體內(nèi)容如下:1.介紹金屬配合物固體熒光材料的研究進展。2.以1,8-萘酐為原料,合成了HL~1和HL~2兩種配體(HL~1和HL~2分別是N-正丁基-4-[(E)-2 (((2-氨基乙基)亞氨基)甲基)苯酚]-1,8-萘酰亞胺,N-正丁基-4-[(E)-2-(((2-氨基乙基)亞氨基)甲基)-6-甲氧基苯酚]-1,8-萘酰亞胺),以及三種新型配合物:[Cu(L~1)_2](1),[Zn(L~1)_2(Py)]_2·H_2O(2)和[Ni(L~2)_2(DMF)_2](3)。研究配合物的熱穩(wěn)定性、固態(tài)熒光性能、及電化學性質(zhì)。熒光實驗的結(jié)果表明:與配體HL~1相比,配合物2有明顯的黃綠色熒光,該發(fā)光現(xiàn)象歸屬為金屬離子微擾的配體發(fā)光,配合物1和3發(fā)生熒光淬滅。3.以2-羥基苯胺、3-吡啶甲酸和4-吡啶甲酸為原料,合成了3-吡啶基苯并惡唑(3-PBO)、4-吡啶基苯并惡唑(4-PBO)兩種配體以及三種新型配合物:[Cd(3-PBO)_2(NO_3)_2(H_2O)_2]CH_3CN(4),[Zn(4-PBO)_2(NO_3)_2](5),[Ag(4-PBO)_2pic]_n(pic=picric acid)(6)。接著對其熱穩(wěn)定性、固態(tài)熒光性能、及電化學性質(zhì)進行研究。金屬配合物的固態(tài)熒光光譜顯示配合物4和5與配體相比分別紅移了12 nm、23 nm,且觀察到明顯的的藍色熒光,這種熒光是由于金屬離子對配體的微擾引起的,而配合物6發(fā)生熒光淬滅。4.以三苯基膦(PPh_3),2,6-雙-氮甲基苯并咪唑基吡啶(mbbp)和以2,6-雙-氮烯丙基苯并咪唑基吡啶(abbp)為配體設(shè)計合成了五種銀配合物,分別是[Ag_4X_4(PPh_3)_4][X=Cl,(7);X=Br,2n(pic)×CH_3CH_2OH(11)。研究了其固態(tài)熒光性質(zhì),最后對其分子內(nèi)的Ag-Ag相互作用進行了討論。熒光實驗的結(jié)果顯示銀簇配合物7-9發(fā)出和配體PPh_3相似的熒光,配合物10和11發(fā)生熒光淬滅。
[Abstract]:Metal complex solid fluorescent materials have been widely used in dye lasers, organic light-emitting diode (OLED), data recording and storage, as well as safe printing and other new fields. With the development of science and the progress of society, some solid fluorescent materials with stimulating response metal complexes have been widely used in dye lasers, organic light-emitting diode (OLED), data recording and storage, as well as safe printing and other new fields. With the development of science and the progress of society, some metal complex solid fluorescent materials with stimulating response have become the focus of attention. This kind of materials can respond to external stimuli by changing some conditions, such as mechanical grinding (force-induced discoloration), heat treatment (thermochromism), light treatment (photochromism), electrification (electrocoloration) and vapor fumigation (gas-induced discoloration). This kind of sensitive material has important practical significance and wide application prospect in information recording, data storage, anti-counterfeiting trademark and optoelectronic devices. Because of their good coordination ability and structural diversity, Naphthimide Shiff base, benzimidazole and benzoxazole derivatives have become the focus of attention. The complexes synthesized from these derivatives not only have easy structure modification, various coordination modes, but also have good luminous properties. Based on the above research background, a series of new complexes were designed and synthesized with Naphthimide Shiff base, benzimidazolyl pyridine and benzoxazolyl pyridine as ligands. The complexes were characterized by infrared spectroscopy, nuclear magnetic resonance hydrogen spectroscopy and X-ray single crystal diffraction. The solid state fluorescence properties and thermal stability of these complexes were also studied. The specific contents are as follows: 1. The research progress of solid fluorescent materials for metal complexes is introduced. 2. HL~1 and HL~2 ligands (HL~1 and HL~2 are N-n-butyl4-[(E)-2 鈮，

本文編號：2502680