本文選題：紅光至近紅外磷光材料 + 銥配合物　； 參考：《吉林大學(xué)》2017年博士論文

【摘要】：有機發(fā)光材料近些年來在顯示、照明、傳感、醫(yī)療和能源等領(lǐng)域扮演著越來越重要的角色。其中基于過渡金屬絡(luò)合物的有機磷光材料,由于其中心存在如銥、鉑等重金屬原子,可以通過強自旋軌道耦合(SOC)和快速系間竄越(ISC)將自身的三線態(tài)和單線態(tài)激子全部用于發(fā)光,將內(nèi)量子效率提升至100%,從而引起了人們極大的興趣。目前綠光、黃光有機磷光材料的效率及壽命已經(jīng)基本能達到產(chǎn)業(yè)化的要求,但是高性能的紅光至近紅外磷光材料仍有待進一步的開發(fā)。金屬銥配合物由于具有磷光壽命較短、發(fā)光效率高、合成提純簡單、光色易調(diào)節(jié)、良好的熱學(xué)及電化學(xué)穩(wěn)定性等優(yōu)點,成為了設(shè)計新型高效紅光至近紅外磷光材料的一個研究熱點。本論文設(shè)計合成了一系列含有脒胍基輔助配體的新型紅光至近紅外磷光銥配合物,對其晶體結(jié)構(gòu)、熱學(xué)性質(zhì)、光物理性質(zhì)、電化學(xué)性質(zhì)、理論計算、載流子傳輸能力等性質(zhì)進行了研究,并基于該系列銥配合物制備了紅光至近紅外磷光電致發(fā)光器件,討論了該系列配合物中材料結(jié)構(gòu)與性能之間的關(guān)系。1、在第二章中,以1-(4-氟苯基)異喹啉,1-(2,4-二氟苯基)異喹啉為第一配體,以脒基配體dipba(N,N′-diisopropylbenzamidinate)為輔助配體合成了兩種新型的深紅光磷光銥配合物SFPIQBA和DFPIQBA,并對這兩個化合物各方面性質(zhì)進行了表征。這種獨特的C··N··Ir··N四元環(huán)配位結(jié)構(gòu)顯著改變了配合物的光電性能,與經(jīng)典輔助配體乙酰丙酮相比,這類脒基輔助配體可以有效提升配合物HOMO能級并且降低能隙,有助于配合物實現(xiàn)深紅光發(fā)射,理論計算表明這兩個配合物的HOMO/LUMO軌道分布較為分離,預(yù)示其具有雙載流子傳輸能力,并通過飛行時間法(time of flight)載流子測試進行了驗證。兩個化合物均具有良好的深紅光發(fā)射(640 nm左右),較高的磷光量子產(chǎn)率和較短的磷光壽命。以SFPIQBA和DFPIQBA為發(fā)光客體制備的電致發(fā)光器件的最大外量子效率和最大功率效率分別為15.4%、9.3lm/W和16.7%、10.4 lm/W,CIE色坐標(biāo)為(0.70,0.30)和(0.69,0.31),即使器件亮度達到了1000 cd/m2時,器件的外量子效率和功率效率仍保持10.6%、3.5 lm/W和10.8%、3.6 lm/W這一較高水平。2、在第三章中,以1-苯基異喹啉作為第一配體,脒基類配體dipba作為輔助配體合成了一種新型的深紅光磷光銥配合物PIQBA。PIQBA具有銥配合物中少見的多晶相現(xiàn)象,分別為730 nm近紅外發(fā)射的晶相A和680 nm深紅光發(fā)射的晶相B。通過對不同晶相中分子間作用力、堆積結(jié)構(gòu)、分子構(gòu)型的分析,研究了兩個晶相之間結(jié)構(gòu)與性能的關(guān)系。脒基類輔助配體dipba中富電子的雙N配位結(jié)構(gòu)對銥配合物分子前線軌道構(gòu)成產(chǎn)生了很大影響,理論計算表明PIQBA具有離域的電子云分布特性,TOF遷移率測試表明了其具有雙載流子傳輸能力。熱學(xué)性質(zhì)表明PIQBA具有良好的熱穩(wěn)定性,有利于真空蒸鍍器件的制備。以化合物PIQBA為發(fā)光客體的器件發(fā)射峰位為676 nm,最大外量子效率為10.7%,最大功率效率為1.9 lm/W,CIE色坐標(biāo)為(0.71,0.28),器件的最大亮度達到5909 cd/m2。表現(xiàn)了非常好的紅光色純度及光譜穩(wěn)定性。3、在第四章中,以7,8-苯并喹啉和1-苯基異喹啉衍生物為第一配體,使用胍基類輔助配體dipig(N,N′-diisoproguanidinate)合成了四種新型紅光至近紅外磷光銥配合物BZQPG、PIQPG、SFPIQPG、DFPIQPG。這系列化合物相比于之前討論的含有脒基輔助配體的配合物有著更加紅移的發(fā)射峰位、更短磷光壽命和更高的磷光量子產(chǎn)率。理論計算表明胍基輔助配體相比于脒基輔助配體給電子能力更強,更有助于提高配合物的HOMO能級,降低配合物能隙。并且與中心銥原子的配位能力也比脒基輔助配體更強,從而有效減少了分子振動能量損失。這四個化合物具有良好的熱學(xué)及電化學(xué)穩(wěn)定性,且擁有高效的雙載流子傳輸能力。以它們做為發(fā)光客體制備的電致發(fā)光器件均表現(xiàn)穩(wěn)定而高效的電致發(fā)光性能,以BZQPG、PIQPG、SFPIQPG和DFPIQPG為發(fā)光客體的器件最大外量子效率分別為27.3%、12.1%、16.3%和16.7%,電致發(fā)光波長分別為592 nm、684 nm、656 nm、652 nm。器件表現(xiàn)了良好的光譜穩(wěn)定性和較小的效率滾降。4、在第五章中,通過在第一配體1-苯基異喹啉上進行簡單的取代基修飾,配合脒胍基輔助配體合成了三種新型近紅外磷光銥配合物MPIQBA、MPIQPG和CF3PIQPG,在不引入更大的共軛基團的情況下將配合物的發(fā)光波長延伸到了近紅外區(qū)域,由于配合物中配體共軛程度的增加往往會引起分子聚集,導(dǎo)致發(fā)光淬滅,所以這種設(shè)計方式有助于獲得高效率的近紅外磷光材料。同時較小的分子量也有利于蒸鍍型電致發(fā)光器件的制備。理論計算表明其HOMO/LUMO軌道分布在不同的基團上,TOF測試表明其具備雙載流子傳輸能力,熱學(xué)和電化學(xué)測試表明三個化合物均具有良好的熱學(xué)和電化學(xué)穩(wěn)定性。以它們作為磷光客體制備了電致發(fā)光器件,其中MPIQBA器件最大發(fā)射波長為688 nm,器件最大外量子效率為12.0%,CIE色坐標(biāo)為(0.71,0.28);MPIQPG器件最大發(fā)射波長為692 nm,器件最大外量子效率達到了11.6%,CIE色坐標(biāo)為(0.71,0.28);CF3PIQPG器件最大發(fā)射波長為692 nm,器件最大外量子效率達到了6.3%,CIE色坐標(biāo)為(0.70,0.28),三個化合物器件的亮度都達到了1500 cd/m2以上。綜上所述,我們合成了一系列新型紅光至近紅外磷光銥配合物,這系列銥配合物的創(chuàng)新點在于使用了新型的脒基和胍基輔助配體,與傳統(tǒng)的乙酰丙酮類輔助配體相比,其富電子的雙N配位結(jié)構(gòu)能夠有效穩(wěn)定中心正三價的金屬銥原子,同時與中心銥原子形成的四元配位環(huán)有著更強的剛性,這樣可以減少分子中由于振動引起的非輻射能量損失,有助于配合物磷光量子產(chǎn)率的提高。理論計算表明,這種脒胍基輔助配體很大程度上參與了配合物的前線軌道構(gòu)成,使銥配合物的HOMO和LUMO軌道分布產(chǎn)生分離,并可以顯著提高配合物分子的HOMO能級,降低配合物能隙。載流子遷移率測試表明這系列銥配合物具有高效的雙極性傳輸能力,可以有效減少電致發(fā)光器件中的三線態(tài)-三線態(tài)淬滅。以這系列配合物制備的器件也均表現(xiàn)出非常好的電致發(fā)光性能,我們通過研究這系列銥配合物中材料結(jié)構(gòu)與性能的關(guān)系,為以后設(shè)計高性能的紅光至近紅外磷光銥配合物提供了新的思路。
[Abstract]:Organic light-emitting materials have been playing a more and more important role in the fields of display, lighting, sensing, medical and energy sources in recent years. Organic phosphors based on transition metal complexes, such as iridium, platinum and other heavy metal atoms, can make their three lines through strong spin channel coupling (SOC) and fast system channeling (ISC). The excitons of the state and single state are all used for luminescence, and the internal quantum efficiency is raised to 100%, which has aroused great interest. At present, the efficiency and life of the yellow light organic phosphor materials have basically reached the requirement of industrialization, but the high performance red to near infrared phosphors still need further development. Due to its short phosphor life, high luminescence efficiency, simple purification, easy adjustment of light and color, good thermal and electrochemical stability, it has become a research hotspot in the design of new high efficiency red to near infrared phosphor materials. A series of new red to near infrared phosphorus containing amidine guanidine assisted ligands was designed and synthesized in this paper. The crystal structure, the thermal properties, the photophysical properties, the electrochemical properties, the theoretical calculation, the carrier transmission capacity and the properties of the carrier transmission are studied. The relationship between the structure and properties of the materials in this series of complexes.1, at second, is discussed. In the chapter, 1- (4- fluoro phenyl) isoquinoline, 1- (2,4- two fluoro phenyl) isoquinoline as the first ligand, and the amid ligand dipba (N, N '-diisopropylbenzamidinate) as the auxiliary ligand, two new types of new dark red phosphorescent iridium complexes are synthesized, SFPIQBA and DFPIQBA, and the properties of the two compounds are characterized. This unique C. N. The N four membered ring coordination structure significantly changed the photoelectrical properties of the complexes. Compared with the classical auxiliary ligands, acetacetone, the amid based ligand could effectively improve the HOMO level of the complex and reduce the energy gap, and help the complex to achieve deep red emission. The theoretical calculation shows that the HOMO/LUMO orbital distribution of the two complexes is relatively separated. It indicates that it has dual carrier transmission capacity and is verified by the carrier test of time of flight (time of flight). All two compounds have good deep red light emission (about 640 nm), high phosphorescence quantum yield and short phosphor lifetime. The largest electroluminescent devices prepared with SFPIQBA and DFPIQBA as luminescent objects The external quantum efficiency and maximum power efficiency are 15.4%, 9.3lm/W and 16.7%, 10.4 lm/W, CIE color coordinates (0.70,0.30) and (0.69,0.31). Even if the device brightness reaches 1000 cd/m2, the external quantum efficiency and power efficiency of the device remain 10.6%, 3.5 lm/W and 10.8%, 3.6 lm/W in this high level.2. In the third chapter, the 1- phenyl isoquinoline is used. For the first ligand, the amid base class ligand dipba is used as the auxiliary ligand to synthesize a new type of deep red phosphorescent iridium complex PIQBA.PIQBA with rare polycrystalline phase in the iridium complex. The crystalline phase A of 730 nm near infrared emission and the crystalline phase B. emitted by the deep red light emission of 680 nm are stacked structures and molecules through the intermolecular interaction in the amorphous phase. The relationship between the structure and the properties between the two crystalline phases is studied. The double n coordination structure of the amitrid based auxiliary ligand dipba has a great influence on the formation of the molecular front-line orbit of the iridium complex. The theoretical calculation shows that the PIQBA has the distribution characteristics of the electron cloud in the field, and the TOF mobility test shows that it has a double carrier transmission. The thermal properties show that PIQBA has good thermal stability and is beneficial to the preparation of vacuum evaporating devices. The emission peak of the device with compound PIQBA as the luminescent object is 676 nm, the maximum external quantum efficiency is 10.7%, the maximum power efficiency is 1.9 lm/W, the CIE color coordinates are (0.71,0.28), and the maximum brightness of the device reaches 5909 cd/m2.. The normal red color purity and spectral stability.3, in the fourth chapter, using 7,8- benzoquinoline and 1- phenyl isoquinoline derivatives as the first ligand, using guanidine auxiliary ligand dipig (N, N '-diisoproguanidinate) to synthesize the new type of red light to near infrared phosphor iridium complex BZQPG, PIQPG, SFPIQPG, DFPIQPG., compared to the series of compounds. The previously discussed complexes with amidamidine assisted ligands have a more red shift emission peak, shorter phosphor lifetime and higher phosphorescent quantum yield. Theoretical calculations show that guanidine assisted ligands are more powerful than amidamidine assisted ligands, and are more helpful to improve the HOMO level of the complexes and to reduce the energy gap of the complexes. The coordination ability of iridium atoms is also stronger than amid assisted ligands, which effectively reduces the molecular vibration energy loss. These four compounds have good thermal and electrochemical stability and have high efficient double carrier transmission capacity. The electroluminescent devices, prepared by them as luminescent objects, show stable and efficient electroluminescence. The maximum external quantum efficiency of the devices with BZQPG, PIQPG, SFPIQPG and DFPIQPG as luminescent objects is 27.3%, 12.1%, 16.3% and 16.7% respectively, and the electroluminescent wavelengths are 592 nm, 684 nm, 656 nm, and 652 nm., showing a good spectral stability and a smaller efficiency rolling down.4 in the fifth chapter, through the first ligand 1- phenyl isoquinoline. Three novel near infrared phosphor iridium complexes, MPIQBA, MPIQPG and CF3PIQPG, are synthesized by simple substituent modification, and the luminescence wavelengths of the complexes are extended to the near infrared region without the introduction of a larger conjugate group. The increase of the ligand conjugation in the complexes often causes the molecules. Aggregation leads to light quenching, so this design helps to obtain high efficiency near infrared phosphor materials. At the same time the smaller molecular weight is beneficial to the preparation of electroluminescent electroluminescent devices. The theoretical calculation shows that the HOMO/LUMO orbit is distributed on different groups, and the TOF test shows that it has dual carrier transmission capacity, thermal and electrical properties. Chemical tests show that the three compounds have good thermal and electrochemical stability. Electroluminescent devices are prepared by them as phosphorescent objects. The maximum emission wavelength of MPIQBA devices is 688 nm, the maximum external quantum efficiency of the device is 12%, the CIE color coordinate is (0.71,0.28), the maximum emission wavelength of the MPIQPG device is 692 nm, and the maximum external device is the device. The quantum efficiency is 11.6%, the CIE color coordinate is (0.71,0.28), the maximum emission wavelength of the CF3PIQPG device is 692 nm, the maximum external quantum efficiency of the device reaches 6.3%, the CIE color coordinate is (0.70,0.28), and the brightness of the three compound devices is above 1500 cd/m2. In conclusion, we have synthesized a series of new red light to near infrared phosphorescent iridium. The innovation of this series of iridium complexes lies in the use of new amidinyl and guanidine assisted ligands. Compared with the traditional acetacetone auxiliary ligands, their electron rich double n-coordination structures can effectively stabilize the central positive trivalent metal iridium atom, and have a stronger rigidity in the four yuan coordination ring formed by the central iridium atom. In order to reduce the non radiation energy loss caused by the vibration in the molecule, it is helpful to improve the phosphor quantum yield of the complexes. The theoretical calculation shows that the amidamidine assisted ligands are largely involved in the front-line orbit of the complexes, separate the HOMO and LUMO orbital distribution of the iridium complexes, and can significantly improve the complex molecules. The HOMO energy level reduces the energy gap of the complex. The carrier mobility test shows that the series of iridium complexes have high efficient bipolar transmission ability and can effectively reduce the three wire state - three line state quenching in the electroluminescent devices. The relationship between the structure and properties of iridium complexes provides a new idea for the design of high performance red to near infrared phosphorescent iridium complexes.

【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4

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