基于1,3,6,8-四甲基咔唑热活化延迟荧光材料的合成及发光性质

本文以1,3,6,8-四甲基咔唑（TMCz）为给体,1,3,4-噁二唑（OXD）和1,3,4-噻二唑（THD）为受体,设计合成了两例发光材料,即TMCz-OXD和TMCz-THD。利用紫外-可见吸收光谱、发射光谱、电化学分析等手段对其光物理、电化学以及电致发光性质进行了研究。实验表明,TMCz的1,8位甲基的空间位阻能有效增大给受体之间的二面角（86°）。TMCz-OXD和TMCz-THD的掺杂膜中均表现出热活化延迟荧光（TADF）性质,相应电致发光的最大外量子效率（EQE）分别为6.5%和6.4%。TMCz可作为蓝光TADF材料的普适性给体,广泛应用于有机光致/电致发光材料以及有机发光二极管等领域。     

含咔唑基团芘类荧光材料的合成与发光性质

以1-溴芘、1,6-二溴芘和9-对乙炔苯基咔唑为原料,通过Sonogashira偶联反应合成了1-[4-(9-咔唑)苯乙炔基]芘和1,6-二[4-(9-咔唑)苯乙炔基]芘两种荧光分子。经熔点、核磁共振氢谱以及元素分析等结构表征,对中间体和目标产物的紫外-可见吸收、荧光发射以及结构与性质之间的构效关系进行了研究。通过结构修饰,可有效调节此类分子的吸收及发射性质。当芘单元作为中心电子受体,以4-苯乙炔基为桥连基,引入咔唑基团作为电子给体时,其分子共轭程度、结构刚性和分子内电荷转移能力显著提高。相对于D-π-A结构的单取代化合物,双取代D-π-A-π-D结构分子的最大发射峰由422 nm红移至446 nm,荧光量子效率由0.64提升至1.08。该类化合物可作为高效的蓝光荧光材料,应用于有机光致/电致发光材料以及有机发光二极管等领域。     

热活化延迟荧光材料的研究与分析

现阶段用于照明的电力消耗约占全球电力消耗的20%左右,如果热活化延迟荧光材料能够得到广泛应用,那么可以显著缓解当前能源需求的压力。从2014年至今,热活化延迟荧光材料蓬勃发展,可见光范围内的热活化延迟荧光材料不断被研发出来,基于热活化延迟荧光材料制备的OLEDs产品已经超过400多种,但热活化延迟荧光材料的发展仍然有许多亟待解决的问题,例如红光热活化延迟荧光材料的EQE还无法超过20%(主要是由于红光材料所需的带隙比蓝绿光更窄,合成更加困难),需要研究者的进一步探索。     

4-氮杂芴-9-酮衍生物的合成及发光性质

以4-氮杂芴-9-酮(IP)为电子受体,咔唑(Cz)为电子供体,通过调节Cz在IP上的取代位置合成了4例荧光染料,即IP-6-Ph Cz、IP-7-PhCz、IP-8-PhCz和IP-9-PhCz。利用紫外吸收光谱、荧光发射光谱、电化学分析等对所得4例荧光染料的光致发光、电致发光以及电化学性质进行了测试。结果表明,IP-6-Ph Cz和IP-9-PhCz分别实现了45.3°和51.8°的大扭曲角,其单重态-三重态能级差(ΔEST)分别为0.32和0.28eV,表现出热活化延迟荧光(TADF)特征,而IP-7-PhCz和IP-8-PhCz仅是普通的荧光染料。其中,IP-7-PhCz的光致发光量子产率(PLQY)为29%,电致发光的最大外量子效率为2.8%。     

MCM-41介孔分子筛负载咔唑类荧光分子杂化材料的合成及发光性质

通过浸渍法将5种咔唑类荧光分子负载于介孔材料MCM-41上,制备有机-无机杂化复合荧光材料,并对咔唑荧光分子和杂化复合材料的表面结构、紫外-可见吸收、荧光发射等性质进行了对比。结果表明,负载后的咔唑类荧光分子分散于MCM-41孔道上,材料热稳定性提高,在100~350℃内没有明显失重,其紫外吸收和荧光发射也发生明显蓝移(λmaxabs=331~368 nm,λmaxem=401~435 nm)。制备的杂化复合材料可用作蓝色荧光材料(λmaxem=401~435 nm)。     

基于硅杂吖啶给体基团的热活化延迟荧光材料的合成与表征

以硅杂吖啶为给体基团,经格氏偶联、Suzuki偶联和Buchwald-Hartwig偶联合成了一种热活化延迟荧光材料5-(4-(4,6-二苯基-1,3,5-三嗪基)苯基)-10,10-二苯基-5,10-二氢硅杂吖啶（DTPDDA）。优化了合成工艺,并对其结构、热稳定性、光学性能进行表征。结果表明,DTPDDA热分解温度378.93℃,玻璃化转变温度320.75℃,具有较高的热稳定性;同时,DTPDDA具有强发光性能,λmax为456nm,是一种蓝光TADF材料。     

含咔唑基团芘类荧光材料的合成与发光性质

以1-溴芘、1,6-二溴芘和9-对乙炔苯基咔唑为原料,通过Sonogashira偶联反应合成了1-（4-（9-咔唑）苯乙炔基）芘和1,6-二（4-（9-咔唑）苯乙炔基）芘两种荧光分子。经熔点、核磁共振氢谱以及元素分析等结构表征,对中间体和目标产物的紫外-可见吸收、荧光发射以及结构与性质之间的构效关系进行了研究。通过结构修饰,可有效调节此类分子的吸收及发射性质。当芘单元作为中心电子受体,以4-苯乙炔基为桥连基,引入咔唑基团作为电子给体时,其分子共轭程度、结构刚性和分子内电荷转移能力显著提高。相对于D-π-A结构的单取代化合物,双取代D-π-A-π-D结构分子的最大发射峰由422 nm红移至446 nm,荧光量子效率由0.64提升至1.08。该类化合物可作为高效的蓝光荧光材料,应用于有机光致/电致发光材料以及有机发光二极管等领域。     

基于1,8-萘酰亚胺延迟荧光材料的合成及性能研究

通过Suzuki交叉偶联反应得到三苯胺和N-苯基咔唑分别取代的1,8-萘酰亚胺衍生物,化合物结构经1HNMR、质谱和元素分析表征。两种材料都是双极分子,存在分子内电荷转移,单线态-三线态能级差分别为0.40和0.32 eV。荧光量子效率和荧光寿命的测试结果表明,两种材料均能发射延迟荧光。     

新型咔唑衍生物的合成及发光性能研究

基于螺二芴的大位阻结构和咔唑的高三线态能级,设计了一种在咔唑的3、4和5、6位并入两个高位阻的螺二芴结构,以4,4′-二甲基联苯为起始原料,经过硝化反应、Bucherer反应、偶联反应、卤化、Suzuki偶联反应和关环等反应成功制备了咔唑衍生物CzSF2,产物结构经过1 HNMR、13 CNMR、MS确证.其在二氯甲烷...     

N-甲基四氢咔唑酮的绿色合成工艺初探

以N,N-二甲基甲酰胺作溶剂,四丁基溴化铵作相转移催化剂,碳酸二甲酯作甲基化试剂,由四氢咔唑酮与氢氧化钾反应先合成钾盐,再经甲基化合成了N-甲基四氢咔唑酮。考察了钾盐与碳酸二甲酯的配比、反应时间、溶剂用量、催化剂及催化剂用量等因素对反应收率的影响。较佳合成条件为碳酸二甲酯∶四氢咔唑酮钾盐=2.5∶1,四丁基溴化铵用量为钾盐物质的量的2%,在100℃反应10h,反应摩尔收率可达80%以上。     

Synthesis and luminescent properties of block copolymers based on polyfluorene and polytriphenylamine

For the preparation of block copolymers containing polyfluorene (PF) and hole transporting segment, PF homopolymers with diphenylamine terminals were synthesized by Suzuki coupling polymerization. The terminals of PF were converted to polytriphenylamine (PTPA) block by C–N coupling polymerization to give PTPA-block-PF-block-PTPA (PF-PTPA) triblock copolymers with different PTPA chain lengths. These polymers were soluble in common organic solvents and readily formed thin films by solution processing. All of the polymers exhibited similar UV absorption and PL emission properties both in chloroform solution and in film state. PF-PTPA block copolymers showed relatively high HOMO compared with that of PF by cyclic voltammetry. Compared with corresponding PF homopolymers, the EL devices based on PF-PTPA block copolymers showed higher luminance and current efficiency than those of PF homopolymers because of the improvement of hole injection by the introduction of PTPA segment.     

稀土高分子配合物发光材料的合成

发光稀土高分子配合物是一类很有价值的功能材料,本文就其3种合成方法进行评述。以稀土离子与含配位基团的聚合物进行反应,难以获得发光强度高的高分子配合物;使稀土离子与高分子配体和小分子配体同时作用,可以得到荧光强度比较理想的产物,但反应难以定量控制;以小分子稀土配合物单体进行聚合反应,也可获得荧光强度较高的高分子配合物,但聚合反应的空间位阻较大。并针对方法3提出了改进的思路。     

Synthesis, characterization, and thermally activated polymerization behavior of bisphenol-S/aniline based benzoxazine

A difunctional benzoxazine monomer, 6,6′-bis(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazinyl) sulfone (BS-a), was synthesized via a solution method from bisphenol-S, aniline and formaldehyde. The chemical structure of the benzoxazine was confirmed by ¹H and ¹³C nuclear magnetic resonance spectroscopy, Fourier transform infrared (FTIR) spectroscopy, elemental analysis, and size exclusion chromatography. The ring-opening polymerization of BS-a monomer was investigated with FTIR under air and nitrogen atmospheres, and with differential scanning calorimetry (DSC) in both dynamic and isothermal conditions. The FTIR results show that the absorption intensities of C-O-C, C-N-C, and oxazine ring decrease gradually with temperature and time rising during the polymerization reaction. The change rates of some absorption intensities of oxazine ring are affected by different atmospheric environments, and a higher degree of conversion is obtained in nitrogen than that in air at the same reaction temperature and in equal time. Kinetic parameters of the dynamic polymerization DSC results were evaluated with Kissinger and Ozawa methods, respectively. The isothermal DSC results show that the polymerization reaction of BS-a monomer follows an autocatalytic mechanism.     

Synthesis and luminescent properties of a novel Eu-containing nanoparticle

We synthesized Eu-containing nanoparticles using the ultra-dilute solution method and characterized by FT-IR, NMR, GPC, DSC, and UV-visible absorption/photoluminescence spectra. The size of Eu-containing nanoparticles was 30-150 nm and the nanoparticles were soluble in common organic solvents. A study of the dependence of emission intensities of the Eu-containing nanoparticles on the Eu content showed that the emission intensities increased nearly linearly with increasing Eu content. In addition, no significant emission concentration quenching phenomenon was observed at the Eu content of 0-9.5 mol%.     

Synthesis of luminescent yttrium silicate materials by the sol-gel method

The sol-gel method is shown to be useful for obtaining luminescent yttrium silicate-based materials with performance characteristics superior to commercial analogs. The effect of the phase composition of sol-gel luminophors on the spectral luminescence parameters is analyzed. A way to prepare materials with controlled granulometric composition is proposed.Translated from Steklo i Keramika, No. 11, pp. 23–26, November, 1996.     

Synthesis, characterization and thermally activated curing of polysulfones with benzoxazine end groups

Polysulfones with benzoxazine end groups (PSU-B-a) were obtained using monomer synthesis method from the phenol terminated polysulfone (PSU-OH), aniline and paraformaldehyde as starting materials. For this purpose, the precursor PSU-OHs with different molecular weights were prepared by condensation of bisphenol-A and bis(p-chlorophenyl) sulfone in presence of potassium carbonate. The structure of the polymers before and after functionalization was confirmed by proton nuclear magnetic resonance spectroscopy (¹H NMR) and Fourier transform infrared spectroscopy (FT-IR). Thermally activated crosslinking behavior of these polymers was investigated by differential scanning calorimetry (DSC). Thermal and tensile properties of the crosslinked polymers obtained from PSU-B-a alone or with low molar mass benzoxazine (P-a) were studied by thermal gravimetric analysis (TGA) and dynamic mechanical analysis (DMA).