| Dehydroabietic acid triarylamine and its derivatives have good fluorescence properties,thermal stability and hole transport properties,and can be used in hole transport materials,fluorescent probes,biological imaging and other fields.In this article,three types of compounds with D-π-A type,D-π-D type and AIE characteristics were constructed using dehydroabietic acid triarylamine as electron donors.Their spectral performance,aggregation-induced emission(AIE)characteristics,electrochemical performance,optimized configuration and molecular frontier orbital energy level,thermal stability and other properties have been studied,the relationship between the molecular structure and properties of the compounds were explored.Their applications in fluorescent probes,perovskite solar cells(PSCs)devices and organic light-emitting diodes(OLED)devices were explored,respectively.The content and results of the study are as follows:(1)A series of D-π-A structure compounds(DTPA-Ⅰ-DTPA-Ⅶ)with dehydroabietic acid triarylamine as electron donor,cyanocetic acid as electron acceptor and a thiophene,benzene,furan ring,etc.as π bridges,were successfully synthesized and characterized by 1H NMR,13C NMR and MALDI-TOFMS.The photophysical properties,optimized configuration,HOMO,LUMO energy levels and band gap values(Eg)of the compounds were also investigated.The results showed that the compounds had a strong absorption peak in the range of 350-550 nm,and a strong emission peak in the range of 400-700 nm.The maximum absorption wavelength(λabs,max)and emission wavelength(λem,max)of compounds with thiophene and furan as π bridge were both red-shifted compared to the compound with benzene as π bridge.The introduction of methyl and hexyl groups on the π bridge made the λabs,max of the compounds blue shift,and ethyl dioxythiophene as the π bridge made the λabs,max of the compound red shift.The compounds all had significant solvatochromism effect.Compounds with thiophene and furan as π bridge had better planarity than compounds with benzene as πbridge,and therefore had a narrower Eg.However,the introduction of methyl and hexyl groups on thiophene and benzene reduced the planarity of the compounds,and the compound obtained a slightly higher Eg.The compounds with ethyldioxythiophene and thiophene as π bridge had similar planarity and higher Eg.When D-π-A type compound DTPA-Ⅰ was used as fluorescent probe to detect water content in solvents dioxane,DMSO and DMF,the fluorescence intensity of DTPA-Ⅰ linearly decreased with the increase of concentration of water in solvents.In the range of 0%to 1%,the fluorescence intensity of DTPA-Ⅰ decreased linearly with the increase of water content,and the detection limit for water content in dioxane was as low as 0.089%.DTPA-Ⅰ with low concentration(0.5 μmol/L)can sensitively detect the water content of polar solvents,and has potential application prospects as a fluorescent probe for detecting water content in polar solvents.(2)Based on dehydroabietic acid triarylamine and methoxytriarylamine,two series of D-π-D compounds(Series 1,2DTPA-CZ1,2DTPA-CZ2 and 2DTPA-CZ3;Series 2,2TPA-CZ1,2TPA-CZ2 and 2TPA-CZ3)were synthesized and characterized by 1H NMR,13C NMR and MALDI-TOFMS.The photophysical properties,optimized configuration,HOMO,LUMO energy levels and band gap values of the compounds,and film surface properties were also studied.The results showed that the compounds had a strong absorption peak in the range of 320-420 nm,and a strong emission peak in the range of 400-500 nm.The introduction of the dehydroabietic acid skeleton and different alkyl substituents on the carbazole group had very little effect on the absorption spectra of these compounds,but made the λem,max of the compounds blue shift.Both series of compounds had significant solvatochromism effects and high quantum yield in THF solution.The introduction of the dehydroabietic acid skeleton and the alkyl chain on the carbazole group slightly reduced the planarity of the compounds,and thus the compounds obtained a slightly higher energy gap value.The T5d values of all compounds were greater than 400℃,and they had good thermal stability.The introduction of dehydroabietic acid skeleton increased the glass transition temperature(Tg)of the compounds and improved their film-forming properties and hydrophobicity,while the introduction of alkyl chains on the carbazole group reduced the Tg of the compounds,and their film-forming properties and hydrophobicity were also slightly worse.Planar non-doped PSC devices 1-6 with ITO/SnO2/CsPbI2Br/HTM/Au structure were prepared using undoped D-π-D compounds as hole transport materials.Device 4 showed the best results,with a VOC of 1.13 V,Jsc of 15.10 mA/cm2,FF of 71.61%,and PCE of 12.27%.This is comparable to the efficiency of 13.41%obtained for the control device prepared using Spiro-OMeTAD.Devices 1-3 did not yield the expected good photovoltaic performance,but the introduction of dehydroabietic acid skeleton improves the stabilities of the devices.(3)Based on dehydroabietic acid triarylamine and triarylamine,three series of AIE characteristic compounds Series 1(TPA-TPE and DTPA-TPE),Series 2(2TPA-TPE and 2DTPA-TPE)and Series 3(DTPAT-AN-XF and 2DTPAT-AN)were synthesized and characterized by 1H NMR,13C NMR and MALDI-TOFMS.The photophysical properties,AIE characteristics,optimized configurations,HOMO and LUMO energy levels and band gap values were studied.For Series 1 and Series 2 compounds,they had a strong absorption peak in the range of 325-400 nm,and a strong emission peak in the range of 400-600 nm.The introduction of dehydroabietic acid skeleton had little effect on the absorption spectrum of the compounds,but it made the λem,max of the compounds red shift in the film state.The compounds all had significant solvatochromism effect and AIE characteristics.Compared with Series 1 compounds,Series 2 compounds had higher HOMO,LUMO energy levels and narrower Eg.The introduction of dehydroabietic acid skeleton made the compounds have better planarity and obtained slightly higher HOMO energy level,lower LUMO energy level and narrower Eg.The compounds had good thermal stability and morphological stability,and the introduction of dehydroabietic acid skeleton made the compounds have better morphological stability.For Series 3 compounds,they had a strong absorption peak in the range of 400-600 nm,and a strong emission peak in the range of 500-800 nm.Both compounds had large Stokes shift,red light emission in solid state and significant solvatochromism effect.DTPAT-AN-XF had AIE characteristics,while 2DTPAT-AN did not have AIE characteristics.The introduction of dehydroabietic acid skeleton made 2DTPAT-AN and DTPAT-AN-XF obtain high HOMO and LUMO energy levels and narrow band gap values.Both compounds had good thermal stability and morphological stability.OLED devices 1-4 with ITO/NPB(40 nm)/EML(20 nm)/TPBi(40 nm)/LiF/Al structure were prepared,in which TPA-TPE,DTPA-TPE,2TPA-TPE and 2DTPA-TPE as luminescent layer.Devices 3 and 4 obtained low starting voltage,high luminance,current efficiency,power efficiency and external quantum efficiency,indicating that an increase in the number of triarylamine derivatives in the compound will improve the performance of the devices.Device 4 showed the best performance,with a Von of 2.2 V,Lmax of 12 414 cd/m2,ηC,max of 6.2 cd/A,ηp,max of 6.5 1m/W and ηext,max of 2.30%.Devices 5-8 with ITO/HTL and EML(40 nm)/TPBi(50 nm)/LiF/Al structure were also prepared,in which compounds are used as hole transport layer and luminescent layer.Compared with Devices 1-4,Devices 5-8 achieved comparable or higher current efficiency,power efficiency and external quantum efficiency,indicating that the compounds can be used as hole transport materials and luminescent materials,which helps to simplify the device structure,shorten the fabrication process and reduce the production cost. |
PDF Full Text Request