二甲氧基蒽－蒽醌体系分子内激发态复合物形成的结构条件与溶剂效应

本文报道了电子给体二甲氧基蒽（ＤＭＡ）和电子受体蒽醌（ＡＱ）以双酚Ａ（ＢＡ）和对苯二酚（ＯＰ）连接起来的双发色团分子的合成和光谱性质研究，并根据光谱数据和荧光光谱，讨论了激发态复合物形成的结构因素和溶剂效应．     

外场作用下蒽分子的激发特性研究

蒽(anthracene)具有良好的热稳定性以及较高的荧光量子产率的优点, 是最早用于研究有机发光器件(organic light-emitting device, OLED)的材料之一. 在本文中, 主要利用量子化学方法研究了不同外电场对蒽分子激发特性的影响规律. 首先采用密度泛函理论(density functional theory, DFT)在6-311G(d, p)基组水平上对蒽分子基态结构进行优化, 基于稳定基态结构, 利用含时密度泛函(time-dependent density functional theory, TDDFT)以及同一基组水平, 计算出蒽分子的前十个激发态的激发能、跃迁偶极矩、振子强度和紫外吸收光谱等数据. 然后以密度泛函B3P86方法优化出的不同外电场下蒽分子基态结构为基础, 使用TDDFT方法研究了不同外电场对蒽分子前线轨道能级和激发特性的影响规律. 结果显示, 无场时蒽分子在紫外区域234.50 nm处有一个较强的吸收峰, 对应基态电子跃迁至第5激发态吸收光子波长; 在外电场作用下, 蒽分子电子由基态跃迁到激发态的各项光谱参数均有显著变化, 加场后蒽分子的吸收光谱发生了红移, 由紫外波段移向了紫外–可见光波段, 与实验值相符合. 分子前线轨道的计算结果也表明蒽分子的最高占据轨道(highest occupied molecular orbital, HOMO)和最低未占据轨道(lowest unoccupied molecular orbital, LUMO)能量差值在不同电场下存在差异. 关键词： 蒽 外电场 激发特性     

蒽、苝和1-氨基蒽醌水溶胶的制备及其荧光性能的研究

用再沉淀法分别制备了蒽、苝和1-氨基蒽醌水溶胶,研究了三者在水溶液中的荧光光谱,通过与其对应的分子荧光光谱比较,发现蒽和苝的水溶胶荧光光谱发生了红移,而1-氨基蒽醌分子从无荧光到它的水溶胶有荧光的转变,根据荧光和分子结构关系,得出3种溶胶是通过分子之间相互重叠聚集而成。同时因为他们为平面型分子,因此π电子共轭度大,使得荧光容易激发和发射,荧光光谱向长波方向移动。     

不同位置取代的三氰基乙烯基蒽的含时密度泛函研究

运用密度泛函理论(DFT)RB3LYP方法和ab initio HF单激发态相互作用(CIS)法分别优化了2-三氰基乙烯基蒽(2-TCVA)和9-三氰基乙烯基蒽(9-TCVA)分子的基态及最低激发单重态几何结构.系统分析了前线分子轨道特征,并探索了电子跃迁机理.应用含时密度泛函理论计算了分子的电子光谱,计算结果与实验值符合得较好.     

晶体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱研究

在强场耦合图像中,采用双自旋-轨道耦合(SO)参量模型建立了过渡族3d2(3d8)离子的三角对称下全组态光谱能级和电子顺磁共振(EPR)公式.与经典的晶体场理论(仅考虑中心金属离子的自旋-轨道耦合作用)相比较,该公式还包括了配体离子的自旋-轨道耦合作用的贡献,这一模型在应用于计算共价性较强的晶体光谱和电子顺磁共振谱可得到合理的结果.作为验证,用完全对角化方法研究了品体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱,结果表明,理论与实验很好地符合.建立的全组态谱能级和电子顺磁共振公式为更精确地计算光谱和电子顺磁共振谱提供了一条可行方法.     

光谱法研究EGCG-Cu(Ⅱ)与ctDNA的相互作用

研究了EGCG-Cu(Ⅱ)-ctDNA系统的荧光光谱,电子吸收光谱和共振光散射光谱(RLS)。与EGCG-Cu(Ⅱ)二元配合物比较,EGCG-Cu(Ⅱ)-ctDNA三元体系光谱显示以下特征：(1)荧光光谱的发射位置没有变,荧光强度显著增强,并且三元体系的荧光强度随着DNA浓度增大而增大。在适宜的条件下,Cu(Ⅱ)-EGCG 配合物有望成为检测ctDNA的荧光探针;(2)电子吸收光谱有明显的增色效应;(3)共振光散射强度也增强。三种光谱的特征显示,EGCG-Cu(Ⅱ)配合物与核酸之间主要依靠插入作用和静电引力结合。由于配合物的插入,使系统的荧光强度增强,而静电作用使其电子吸收光谱和共振光散射光谱产生增色效应。酸度和离子强度对三元系统荧光强度的影响也进行了实验和讨论。     

光转换有机白光发光二极管发光性能研究

研究一种有机白光发光材料,采用热熔法制备出有机薄膜(核黄素、蒽酮衍生物和线性低密度聚乙烯)。研究结果表明：核黄素、蒽酮衍生物和线性低密度聚乙烯的配比和制膜的加热时间对有机薄膜的发光光谱具有一定影响;得到了从绿光到红光的宽带光谱;用此薄膜封装成白光发光二极管的性能良好。     

螺芴氧杂蒽LB膜的制备及光谱特性研究

为了研究聚芴材料DSFX-SFX分子在气液两相表面的行为,分子处于溶液、LB膜及粉末状态的光学特性,以及分子有序排列对其发光特性的影响,制备了聚芴材料DSFX-SFX的X型LB膜,研究了π-A等温曲线,测量了其紫外-可见吸收谱和稳态荧光光谱。结果表明,分子以face-on形式平躺在亚相表面,单分子面积为4.78 nm2。在氯仿溶液中吸收峰位在354 nm,归属于分子中三聚氧杂蒽部分与芴环间π-π*电子跃迁;荧光发射峰位在396,419,445 nm(肩峰),归属于发色团三聚氧杂蒽,是芴环与氧杂蒽环之间的电荷转移。在LB膜中,吸收谱和荧光光谱与其溶液光谱相比,整体红移6 nm。结果表明:在LB膜中,两个分子形成激基缔合物,与单分子状态相比,激基缔合物的HOMO升高而LUMO降低。与粉末状态相比,该材料在LB膜中有很强的荧光发射,表明该材料形成有序排列超薄膜有利于荧光发射。     

恒能量同步荧光法快速同时测定蒽和9, 10-二甲基蒽

建立了蒽和9,10-二甲基蒽的同时恒能量同步荧光分析法。它们的恒能量同步荧光光谱和常规荧光光谱相比,分辨力明显提高。蒽和9,10-二甲基蒽的线性范围分别为0～2 μg·mL-1和0～5 μg·mL-1,检出下限分别为2.2 ng·mL-1和1.7 ng·mL-1, 相对标准偏差不大于2%。水样中蒽和9,10-二甲基蒽的回收率为85%～103％。该方法简便快速,无需预分离。     

基于电子倍增的高光谱成像链模型的系统信噪比分析

高光谱成像的应用效果非常依赖于所获取的图像信噪比(SNR)。在高空间分辨率下,帧速率高、信噪比低,由于光谱成像包含了两维空间-光谱信息,不能使用时间延迟积分(TDI)模式解决光能量弱的问题;目前多采用摆镜降低应用要求,但增加了体积和质量,获取的图像不连续,且运动部件降低了航天的可靠性。基于此,将超高速电子倍增与成像光谱有机结合,构建了基于电子倍增的高分辨率高光谱成像链模型,综合考虑辐射源、地物光谱反射、大气辐射传输、光学系统成像、分光元件特性、探测器光谱响应和相机噪声等各个环节,可用于成像链路信噪比的完整分析。采用LOWTRAN 7软件进行大气辐射传输计算,对不同太阳高度角和地物反射率计算像面的照度,根据电子倍增电荷耦合器件(EMCCD)探测器的噪声模型,计算出不同工作条件下的SNR。对SNR的分析和实验,选择适当的电子倍增增益,可使微弱光谱信号SNR提高6倍。     

TADF激基复合物主体材料提升溶液法制备蓝色荧光有机发光二极管的效率

为了提升溶液法制备的蓝色荧光有机发光二极管(OLEDs)的效率,采用了基于热激活延迟发光(TADF)的激基复合物作为主体材料。TADF激基复合物主体可以利用反向系间窜跃上转换形成单线态激子并将能量传递到客体,从而可以同时利用发光层中的三线态激子和单线态激子,以提升蓝色荧光器件的效率。选择蓝色荧光材料1-4-Di-[4-(N,N-diphenyl)amino]styryl-benzene(DSA-ph)作为客体发光材料,4,4′,4″-T-ris(carbazol-9-yl)triphenylamine(TCTA)掺杂1,3,5-Tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)(TPBi)作为热激活延迟荧光激基复合物主体,通过溶液法制备了蓝色荧光OLEDs。通过测试TCTA,TPBi以及TCTA掺杂TPBi的光致发光光谱发现,与TCTA和TPBi相比,TCTA掺杂TPBi的光致发光谱(PL)发生了明显的红移(峰值波长变为437 nm),而且光谱变宽,证明了TCTA∶TPBi激基复合物的形成。通过对于DSA-ph掺杂激基复合物主体的薄膜与DSA-ph掺杂poly(methyl methacrylate)(PMMA)的薄膜进行PL测试发现,两者发光峰相同,都是来自DSA-ph的发光,说明激基复合物主体将能量传递到了DSA-ph;DSA-ph的吸收光谱与激基复合物主体的PL光谱存在很大重叠,说明激基复合物主体与DSA-ph的能量传递非常有效;通过对激基复合物主体掺杂不同浓度客体的薄膜进行瞬态PL衰减测试发现,与纯DSA-ph的寿命相比,DSA-ph掺杂激基复合物主体之后其寿命会延长,纯DSA-ph的寿命只有1.19 ns,DSA-ph掺杂激基复合物主体的荧光衰减曲线与激基复合物主体的荧光衰减曲线相似,这进一步证明了激基复合物主体将能量传递到了DSA-ph。研究了主体引入以及DSA-ph掺杂浓度对器件性能的影响。对于器件的亮度、电流密度、电压、电流效率、电致发光光谱等参数进行了测试,与不采用激基复合物主体的器件相比,采用激基复合物主体的器件性能明显改善,在DSA-ph掺杂浓度为10%时,器件亮度从2133.6 cd·m^-2提升到了3597.6 cd·m^-2,器件效率从1.44 cd·A-1提升到了3.15 cd·A-1,发光峰只有来自DSA-ph的发光。采用TADF激基复合物主体的方法有潜力实现溶液法制备的高效蓝色荧光OLEDs。     

用荧光探针签别CYP2C9*3基因

用一种基激复合物荧光探针系统来签别碱基错配的CYP2C9*3基因,该系统选择两个分开的与靶点碱基相对应的12碱基荧光标记的寡核苷酸作为探针,分别对24碱基、47碱基、质粒(3165bp)的靶点CYP2C9基因和CYP2C9*3基因进行杂交配对,结果该基激复合物荧光探针系统能有效签别各种长度的CYP2C9基因和CYP2C9*3基因,背景干扰很低,灵敏度高,可尝试用于其他基因型的遗传多态性的签别。     

Fluorescence study of inter- and intramolecular interactions in poly(p-N,N-dimenthylaminostyrene-co-9-vinylantracene)

A new exciplex-forming polymer, poly(p-N, N-dimethylaminostyrene-co-9-vinylanthracene) (PDMA-AN, DP ≈ 25) was prepared by copolymerization of p-N, N-dimethylaminostyrene and 9-vinylanthracene. Exciplex formation was observed both in the fluid media and a polymer film. The fluorescence spectrum of PDMA-AN is characterized by the appearance of a high-energy exciplex formed by the neighboring pendant 9-anthryl (AN) and p-N, N-dimethylanilino (DMA) groups, which is shifted by approximately 85 nm to shorter wavelengths in comparison with the emission band of the intermolecular exciplex formed by the monomer model anthracene-p-N, N-dimethylaminotoluene (DMAT). The polymer conformation appropriate for the formation of this state exists prior to the initial excitation and is partially eclipsed. The effects of concentration and polarity of the solvent on the flourescence emission are discussed. A red shift of the maximum wavelength of the flourescence band as a function of concentration was found in a nonpolar solvent (toluene). However, in a relatively polar solvent (1,2-dichloroethane), a shoulder peak at a longer wavelength gains in intensity with increasing concentration. These phenomena are attributed to the increase of the contribution of the normal intermolecular exciplex state in which the interacting AN-DMA groups achieve an eclipsed and sandwiched conformation.     

激基复合物给体作间隔层对激子复合区域的调节

为研究激基复合物器件激子复合区域的变化,在TPD/BPhen界面可形成激基复合物发光的基础上,以Ir(pq)2(acac)为探测层,制备器件ITO/Mo O_3(2.5 nm)/TPD((40-x)nm)/Ir(pq)2(acac)(0.5 nm)/TPD(x,x=0,3,6,10 nm)/BPhen(40 nm)/Cs2CO_3/Al,其中靠近BPhen的TPD称之为间隔层。电致发光光谱表明,该组器件的激子复合区域主要位于Ir(pq)2(acac)薄层和TPD/BPhen界面,分别发射595 nm和478 nm的光。随着TPD间隔层厚度的增加和电压的升高,发光区域向激基复合物区域(TPD/BPhen界面)移动,即更多的电子和空穴在TPD/BPhen界面形成激基复合物发光,Ir(pq)2(acac)发光减弱。当间隔层厚度由0 nm增至10nm时,6 V电压下的Ir(pq)2(acac)和激基复合物发光强度的比值由44降至1.5。对于间隔层厚度为6 nm的器件,Ir(pq)2(acac)和激基复合物发光强度的比值由6 V时的2.8降至10 V时的1.0。由此可见,激基复合物给体作间隔层能有效调节激子复合区域。     

Magnetic field effect on indole exciplexes: an anomalous dielectric dependence

Individual exciplex formation between various aromatic hydrocarbons, anthracene, pyrene, all-s-trans-1,4-diphenylbuta-1,3-diene and a heteroaromatic amine, 1,2-dimethylindole, was investigated by steady-state fluorescence and magnetic field effect (MFE). A comparative study was carried out with two other exciplex systems 9-cyanophenanthrene-1,2-dimethylindole and 9-cyanophenanthrene-N-methylindole. The extent of charge transfer and dielectric dependence of MFE reveals the potential role of specific interactions related to exciplex geometry.     

Structural effects on intramolecular exciplexes of 1-amino-3-anthryl-(9)-propanes

The photophysical behavior of six 1-(N-aryl-N-alkyl)-amino-3-anthryl-(9)-propanes was studied by steady-state and time-resolved fluorescence measurements in methylcyclohexane/ isopentane (MP). Structurally, these compounds are most suitable for the formation of intramolecular exciples as shown by the high exciplex quantum yields. The rate constants and the activation energies show that the rate of the exciplex formation depends on steric effects of the N-alkyl group and on the donor effect of the N-aryl group. From the rise curves of the exciplex emission it follows that also in nonpolar solvents exciplexes with a conformation deviating from the favored sandwich structure can be formed. The solvent effect on the fluorescence properties was investigated.     

Exciplex elimination in an organic light-emitting diode based on a fluorene derivative by inserting 4,4’-N,N’-dicarbazole-biphenyl into donor/acceptor interface

Organic light-emitting diodes (OLEDs) composed of a novel fluorene derivative of 2,3-bis(9,9-dihexyl-9H-fluoren-2-yl)-6,7-difluoroquinoxaline (F2Py) were fabricated, and exciplex emission was observed in the device. To depress the exciplex in an OLED for pure colour light emission, 4, 4'-N,N'-dicarbazole-biphenyl (CBP) was inserted as a separator at the donor/acceptor interface. It was found that the device without the CBP layer emitted a green light peaking at 542~nm from the exciplex and a shoulder peak about 430~nm from F2Py. In contrast, the OLED with CBP layer emitted only a blue light peak at about 432~nm from F2Py. Device efficiencies were calculated by a simulative mode in an injection controlled type mechanism, and the results showed that exciplexes yield much lower quantum efficiency than excitons. The device with CBP has a higher power efficiency as no exciplex was present.     

Analysis of the Effects of Protic,Aprotic, and Multi-Component Solvents on the Fluorescence Emission of Naphthalene and its Exciplex with Triethylamine

The emission spectra of naphthalene (NP)–triethylamine (TEA) systems were measured under steady-state illumination conditions in some protic and aprotic solvent-tetrahydrofuran (THF) mixtures. The fluorescence spectrum of the NP–TEA system in THF could be separated into two component bands (band A at 329 nm (fluorescence of NP) and band B at 468 nm (emission from an intermolecular exciplex)). The intensities of bands A and B decreased with increasing solvent polarity. The intensity of band B also decreased owing to the hydrogen-bonding interaction between TEA and protic solvents, but in this case the intensity of band A increased. The decrease in the intensity of band A with increasing solvent polarity is considered to be caused by the enhanced formation of an ion-pair parallel to the formation of an exciplex with increasing solvent polarity. The decrease in the intensity of band B is considered to be caused by the enhanced formation of ion-pair both parallel to and through the formation of the exciplex. The increase in the intensity of band A and the decrease in that of band B upon the addition of protic solvents is caused by the decrease in the concentration of free TEA. Acetonitrile only has a polar effect and trichloroacetic acid only has a hydrogen-bonding (protonation) effect, while alcohols have both the effects.     

激基复合物和磷光超薄层相结合的高效率非掺杂白光有机发光二极管

将蓝光激基复合物mCP∶PO-T2T和磷光超薄层结合,分别制备了基于Ir（pq）₂acac（～0.5 nm）/mCP∶PO-T2T/Ir（pq）₂acac（～0.5 nm）结构的双色互补色和基于Ir（ppy）₃（～0.5 nm）/mCP∶PO-T2T/Ir（pq）₂acac （～0.5 nm）结构的三基色非掺杂白光有机发光二极管（White organic light emitting diodes, WOLED）,以探索超薄层在激基复合物中的应用。所制备的双色互补色WOLED,其最大电流效率、功率效率和外量子效率分别为46.1 cd/A、43.9 lm/W和22.2%,而三基色WOLED所实现的最大电流效率、功率效率和外量子效率分别为66.8 cd/A、63.5 lm/W和24.2%。研究分析表明,从高能的蓝光激基复合物发光层向两侧低能的红光和绿光磷光超薄层有效的能量传递是实现非掺杂WOLED高效率的原因。