蒽衍生物蓝光材料的合成与光谱分析

采用还原4-甲苯基锂和β-萘基锂与2-氯蒽醌的加成物制备了有机电致蓝光材料2-腈基-9,10-二(4-甲苯基)蒽和2-腈基-9,10-二(β-萘基)蒽(简称BA和NA)。通过红外、核磁共振、质谱、元素分析对其结构进行了表征。利用紫外可见吸收光谱、荧光光谱研究它们的发光性能。紫外光谱表明BA和NA都有2个吸光带,其中BA的E带波长为272nm,B带有3个吸收峰,其波长分别为369nm、392nm、413nm;NA的E带波长270nm,B带的3个吸收波长分别为372nm、393nm、413nm。采用413nm的激发光技法,BA和NA的荧光发射峰波长分别为437nm,442nm,半峰宽为56nm和57nm,有很好的蓝光色纯度。     

有机电致发光材料双萘基蒽的合成及表征

采用蒽,9-溴蒽,1-萘硼酸,2-萘硼酸为原料,NBS为溴化试剂,通过Suzuki偶联反应制备出9,10-二(1-萘基)蒽(α-ADN)、9,10-二(2-萘基)蒽(β-ADN)及9-(1-萘基)-10-(2-萘基)蒽(α,β-ADN),收率分别为96.10%、97.82%和95.60%,液相色谱检测纯度均98%以上,通过红外光谱对其主体骨架结构进行了表征。利用紫外-可见吸收光谱进行了紫外吸收表征,表明三种ADN有2个吸收带,其中E带有2个吸收峰,波长分别为232nm、259～264nm;B带有3个吸收峰,其波长分别在359nm、377nm、398nm附近。通过热重分析表明三种ADN结构的化合物均具有很好的热稳定性。     

9,10-二(β-萘基)蒽-2-硼酸的合成研究

以2-溴-9,10-二(β-萘基)蒽为原料,在低温条件下得到9,10-二(β-萘基)蒽-2-硼酸,并通过核磁共振、红外光谱分析、元素分析、质谱分析对其结构进行了确认和表征。并探讨了不同反应条件对收率的影响,确定了反应的最佳条件为:在-78℃下,以叔丁基锂作为锂试剂,以物质的量比为n(卤代芳烃)∶n(锂试剂)∶n(硼酸酯)=1∶5∶6,分别滴加叔丁基锂、硼酸三异丙酯,收率可达76.80%。     

2-苯基-9,10-双取代蒽的合成研究

采用2-溴蒽醌,溴苯,2-溴萘为原料,丁基锂为锂化试剂,通过对羰基加成还原再发生Suzuki偶联,反应制备出2-苯基-9,10-双苯基蒽和2-苯基-9,10-双(2-萘基)蒽,收率分别为96.40%和95.70%,液相色谱检测纯度(254nm)为99.42%和99.40%,通过红外光谱对其主体骨架结构进行了表征。热重分析表明苯环结构越多,化合物热分解温度越高。少量2-苯基-9,10-双苯基蒽或2-苯基-9,10-双(2-萘基)蒽溶解在溶剂中,在自然环境中肉眼即可观察到较强的蓝色荧光。     

蓝光材料2-叔丁基-9,10-二（9,9-二正丙基芴基）蒽的合成与性能表征

本文设计并合成了一种新型蒽衍生物蓝光材料2-叔丁基-9,10-二（9,9-二正丙基芴基）蒽.化合物中引入的柔性烷基链有效抑制了分子间的相互作用,使该化合物不易结晶,同时提高了化合物在有机溶剂中的溶解度.通过量子力学方法计算发现,化合物具有顺反两种稳定构型,分子的平面性差,能减弱分子间相互作用.化合物在二氯甲烷溶液中的最大荧光发射峰在443 nm,在环己烷溶液中测得荧光量子效率为0.78,固态薄膜的最大发射峰波长相对溶液有少量红移（450 nm）.热失重和差热分析结果表明,该化合物具有较高的热稳定性,分解温度和玻璃化转变温度分别为365℃和126℃.     

蓝色发光材料9,10-二(α-萘基)蒽的合成

以二-二苯基膦二茂铁二氯化钯(PdCl2(dppf))为催化剂,9,10-二溴蒽和α-萘硼酸为原料,采用Suzuki偶联法合成蓝色发光材料9,10-二(α-萘基)蒽。考察了反应条件,如催化剂用量、溶剂、碱、反应温度、α-萘硼酸与9,10-二溴蒽比率等对反应收率的影响,得出最佳的反应条件是:甲苯/乙醇/水体系(体积比6/1/2);α-萘硼酸与9,10-二溴蒽的物质的量比为3;催化剂量占卤代芳烃的0.5mol%;以碳酸钾为碱,反应7h,收率达到98%,结果远远好于常用的四-三苯基膦钯(Pd(PPh3)4)催化剂。产品经重结晶纯化后,纯度达99%以上,可直接用于OLED器件。     

苯炔参与的N-桥环衍生物的合成

本文报道一类N-桥环衍生物（化合物4a～6）的合成方法。以4-溴-2-（溴甲基）苯甲醛（1）为原料，分别和两种胺（甲胺、苄胺）反应，得到两种二烯中间体：5-溴-2-甲基-2H-异吲哚（2a）和2-苄基-5-溴-2H-异吲哚（2b），苯炔前体化合物[5-（甲氧羰基）-2-（三甲基硅）苯基]（苯基）碘鎓三氟甲烷磺酸盐（3）再分别与两种二烯中间体（2a）和（2b）反应得到7-溴-11-甲基-9,10-二氢-9,10-环亚胺蒽-2-甲酸甲酯（4a）和7-溴-11-苄基-9,10-二氢-9,10-环亚胺蒽-2-甲酸甲酯（4b），其中，化合物（4b）脱除苄基得到7-溴-9,10-二氢-9,10-环亚胺蒽-2-甲酸甲酯（5），化合物（5）与乙酰氯发生N-酰基化反应得到7-溴-11-乙酰基-9,10-二氢-9,10-环亚胺蒽-2-甲酸甲酯（6）。中间体及产物结构经1H NMR和LC-MS表征。同时以（4a）的合成为模型，考察反应条件对该Diels-Alder反应收率的影响，确定最佳反应条件为：物料摩尔比n(2a)∶n(TBAF)∶n(3)=2.0∶2.0∶1；反应溶剂为二氯甲烷；反应温度为0℃；反应时...     

新型芳香多羧酸的合成及荧光性质

芳香多羧酸常用于构筑金属有机框架(MOFs)材料,为了增加MOFs材料的比表面积,从而提高材料对气体的吸附性能,分别以1,3,5-三溴苯和9,10-二溴蒽为原料,通过Suzuki偶联反应设计合成两个芳香多羧酸配体,即3,3'-(9,10-蒽二基)-二苯甲酸和三-(3'-羧基苯基)苯(H3TCPB),其中前者为新化合物,其结构经1HNMR、13CNMR和HRMS表征。由于含蒽材料具有强荧光性能,研究了3,3'-(9,10-蒽二基)-二苯甲酸的固体室温UV/Vis和荧光激发光谱。结果表明,该化合物的最大吸收λmax为252和366 nm,最大发射波长为428 nm,具有发紫光的性质。使用配体H3TCPB和锌盐水热合成一个MOF,即{[Zn4(TCPB)2(OH)2(CH3OH)(DMF)3]·2DMF·H2O}∞。BET比表面积测试结果表明,其比表面积为290 m2/g。     

聚硅烷电致发光材料的研究

采用Würtz反应合成了两种同时具有σ-共轭结构和π-共轭结构的聚硅烷:聚二甲基硅烷9,10-共蒽聚合物{([)(Me2Si)3An(])n}和聚甲基苯基硅烷9,10共蒽聚合物{([)(MePhSi)2An(])n},并用红外光谱、1H核磁共振谱和凝胶色谱表征了其结构,用紫外光谱测试了其紫外吸收性能.结果表明,用波长为254 nm的紫外线照射浓度为2×10-3mol/L的聚二甲基硅烷共蒽聚合物甲苯溶液时,其紫外吸收没有变化;聚甲基苯基硅烷9,10-共蒽聚合物的UV光谱的最大吸收波长(λmax)(377.2 nm)比聚二甲基硅烷9,10-共蒽聚合物的λmax(376.4 nm)更长,因此稳定性更好.     

一种含氧桥环结构的蒽衍生物的合成

以1,2,4-三溴苯(2)为起始原料,在正丁基锂作用下原位生成苯炔中间体,与呋喃发生Diels-Alder反应,得到6-溴-1,4-二氢-1,4-环氧萘(3);化合物3再与3,6-二(吡啶-2-基)-1,2,4,5-四嗪(4)发生逆Diels-Alder反应,得到5-溴异苯并呋喃(5);最后,[5-(甲氧羰基)-2-(三甲基硅)苯基](苯基)碘鎓三氟甲烷磺酸盐(6)所形成的苯炔中间体与化合物5发生Diels-Alder反应,得到目标化合物7-溴-9,10-二氢-9,10-环氧蒽-2-甲酸甲酯(1)。对目标化合物1进行衍生化研究发现,目标化合物1经过插羰反应,得到9,10-二氢-9,10-环氧蒽-2,7-二甲酸二甲酯(7)。各化合物结构均经¹HNMR和ESI-MS确证。该研究为含氧桥环结构的蒽衍生物的合成提供了参考。     

红色荧光粉Ca2La8Si6O26:Eu的制备和性能

采用高温固相法合成新型CaeLasSi6O26:Eu红色荧光粉,利用X射线衍射、扫描电镜及荧光光谱对其进行了表征.结果表明:合成的Ca2LasSi6O26:Eu属于六角晶系,可被近紫外光(394 nm)和蓝光(464 nm)有效激发,发射峰值位于614 nm(对应于Eu3+的5D0→7F2跃迁),激发波长与目前广泛使用...     

Ca2B5O9Cl:Eu2+蓝色荧光粉的发光特性

采用高温固相法合成了Ca2B5O9Cl:Eu2 蓝色荧光粉,并对其发光性质进行了研究.该荧光粉在近紫外370 nm激发下的发射光谱为峰值位于453 nm的宽带发射,对应了Eu2 的4f65d→4f78S7/2特征跃迁发射.监测453nm的发射峰,得到其激发光谱为250～450nm的宽带,与产生350～410nm辐射的紫外发光二极管(ultraviolet light-emitting diode,UV-LED)管芯匹配很好.当CaCl2用量为理论用量的1.1倍,H3BO3用量为理论用量的1.3倍,Eu2 掺杂浓度为6%时,蓝光发射最强.Ca2B5O9Cl:Eu2 是适合UV-LED管芯激发的白光发光二极管用高亮度蓝色荧光粉.     

Comparative analysis on the photoluminescence properties of Cs2BF6:Mn4+ (B = Ge,Si, Zr,Ti) red phosphors for WLEDs

A series of Cs₂BF₆:Mn⁴⁺ (B = Ge, Si, Ti, Zr) red phosphors were synthesized by a precipitation-cation exchange route. The phase purity, morphology, and constituent were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Optical properties were investigated by photoluminescence (PL) spectra and high-resolution PL. Temperature-dependent PL examination at the range of both 273-573 K and 10-300 K was performed to investigate the emission mechanism of Mn⁴⁺ in these fluorides. The intensity for both zero-phonon lines (ZPLs) and vibration coupled emission of Mn⁴⁺ in these four systems with different crystal structures was investigated systematically. These phosphors present bright red emission under blue light (467 nm) illumination, among which Cs₂GeF₆:0.1Mn⁴⁺ shows the highest emission intensity with ultrahigh quantum efficiency of 94%. The white light-emitting diodes (WLEDs) fabricated with this sample, blue InGaN chips and commercial YAG:Ce³⁺ phosphor exhibited high luminous efficacy beyond 100 lm/w with high color rendering index (~88.6) and low color temperature (~3684 K).     

ZnO-TiO2纳米纤维的制备及亚甲基蓝的太阳光催化降解

以钛酸四丁酯〔Ti(OC4H9)4〕、硝酸锌和聚乙烯吡咯烷酮(PVP)为原料,采用溶胶-凝胶法和静电纺丝法制备无机有机复合的PVP/ZnO-TiO2纤维,高温焙烧制得直径100～200 nm的ZnO-TiO2纳米纤维。通过差动-热重(DSC-TGA)、傅里叶变换红外光谱(FTIR)、扫描电镜(SEM)等进行了表征,并测定了其对亚甲基蓝溶液的太阳光催化性能。结果表明,w(ZnO)=3%时,ZnO-TiO2纳米纤维对亚甲基蓝催化活性最高,太阳光照射6 h后降解率达99.4%,重复使用8次降解率仍然在95%以上。     

Synthesis and electroluminescence property of new hexaphenylbenzene derivatives including amine group for blue emitters

Three new blue-emitting compounds of 5P-VA, 5P-VTPA, and 5P-DVTPA for organic light-emitting diode (OLED) based on hexaphenylbenzene moiety were demonstrated. Physical properties by the change of the substitution groups of the synthesized materials were systematically examined. Photoluminescence spectrum of the synthesized materials showed maximum emitting wavelengths of about 400 to 447 nm in solution state and 451 to 461 nm in film state, indicating deep blue emission color. OLED devices were fabricated by the synthesized compounds using vacuum deposit process as an emitting layer. The device structure was ITO/2-TNATA 60 nm/ NPB 15 nm/ EML 35 nm/ TPBi 20 nm/ LiF 1 nm/ Al 200 nm. External quantum efficiencies and CIE values of 5P-VA, 5P-VTPA, and 5P-DVTPA were 1.89%, 3.59%, 3.34%, and (0.154, 0.196), (0.150, 0.076), (0.148, 0.120), respectively. 5P-VTPA and 5P-DVTPA exhibited superior highly blue quality and thermal property such as high T_d of 448°C and 449°C.     

含咔唑基聚合物的合成、发光性能及应用

采用封管聚合法合成了3种含咔唑基聚合物——聚乙烯基咔唑(PVK)、聚2-(9-咔唑基)乙基甲基丙烯酸酯(PCEM)和聚N-〔3-(9-乙基咔唑基)〕甲基丙烯酰胺(PECMA),考察了其紫外光谱和荧光光谱,探讨了取代基对咔唑基团发光性能的影响。结果表明,单体CEM和ECMA表现出明显的结构自猝灭效应(SSQE),而相应的聚合物未见SSQE。单体乙烯基咔唑(NVK)、CEM的荧光最大发射波长分别为440、435 nm,相对于咔唑(418nm)有明显的红移,ECMA则蓝移(410 nm),而相应的聚合物红移或蓝移都不明显。将聚合物作为空穴传输材料,通过共聚引入8-羟基喹啉铝高分子后,8-羟基喹啉铝高分子发光材料的电致发光起亮电压由14 V下降至9V,发光效率提高了3~4倍。     

An alternating copolymer for a blue light-emitting diode

An alternating copolymer composed of 9,9′-dihexylfluorene and N-2-ethylhexyl carbazole was synthesized to use as an emissive polymer in a light-emitting diode (LED). The copolymer is soluble in organic solvents and spin-cast to make a fine film. An LED fabricated by sandwiching the alternating copolymer between indium-tin oxide and aluminum emits a white color with the full width at half maximum of 150 nm. The electroluminescence spectrum becomes simplified to have an emission peak at 460 nm for fine blue color when the copolymer is blended with poly(vinylcarbazole) with a ratio of 1 to 4 before the use as an emissive layer. The forward bias turn-on voltage for the LED is 13, and quantum efficiency is 0.002%. Received: 21 October 1996/Revised: 6 November 1996/Accepted: 19 November 1996     

Wide-band blue-emitting in Ce3+ doped Ca2YZr2Al3O12 garnet-type phosphor designed via local structural lattice distortion and synthesized in nonreducing atmosphere

It is of great significance to explore blue photoluminescent phosphor for white light-emitting diodes excited by near-ultraviolet chip. However, it is very challenging to prepare efficient blue luminescence in phosphor by an unsophisticated synthesis process. In this work, a series of blue-emitting Ca₂Y_1-xZr₂Al₃O₁₂: xCe³⁺ phosphors are designed via local lattice distortion and synthesized in nonreducing atmosphere. The crystal structure of samples and the coordination environment of Ce³⁺ have been investigated in detail by X-ray diffraction and Rietveld refinement method. The wide-band blue emission peaking at 460 nm is attributed to a relaxed crystal field strength. Based on dodecahedron distortion caused by unequal increase of Ce–O bond length, the wavelength of blue color luminescence tuning can be realized from 459 nm to 472 nm. In addition to the concentration quenching effect, the fluorescent lifetimes, thermal quenching effect, the internal quantum efficiency, CIE chromaticity coordinates and related mechanisms of samples have also been studied systematically. Using the representative sample with other tricolor phosphors on a 365 nm chip, a prototype LED device with chromaticity point of (0.394, 0.384) and high CRI (93.5) at CCT of 3755 K is fabricated. All the results suggest that Ca₂Y_1-xZr₂Al₃O₁₂: xCe³⁺ phosphors can be conducted as potential alternative of blue-emitting phosphor for near-ultraviolet pumped white light-emitting diodes.     

Synthesis and Characterization of Un-doped Deep-Blue Organic Light-Emitting Materials Containing Spirofluorene and Biphenyl or Substituted Biphenyl

A series of novel blue light-emitting materials, spirofluorene derivatives, DBSF, 3DBSF, and 5DBSF, based on 2′,7′-dibromospiro- [benzo[c]fluorene-7,9′-fluorene] (DBrSPFF) were successfully synthesized and identified by IR, ¹H-NMR, and¹³C-NMR, MS. Optical properties were examined by UV-Vis absorption spectra and photoluminescence (PL) emission spectra. They performed great blue light characteristics. PL quantum yield was calculated by using quinine sulphate in 0.1M H₂SO₄ as standard. Electro-chemical behavior was examined through cyclic voltammeter measurement. They may be potential promising blue light-emitting materials for OLED.     

高效液相色谱测定40%乙烯利中6-苄氨基嘌呤方法的研究

首次建立了高效液相色谱测定40%乙烯利中6-苄氨基嘌呤含量的方法.色谱柱为Symmetry C18(150 mm×3.9 mm×5 μm);流动相为甲醇-水(V/V=50:50);流速为0.8 mL/min;线性回归方程为y=9.35×106x-3.52×103,r=0.999 8,线性范围为32.9～411 μg;加标回收率平均值为98.2%,RSD为1.42%.