Infrared Luminescence of Ytterbium Ion in Complexes with Calix[4]resorcinarenes

New ytterbium complexes with seven calix[4]resorcinarenes containing methoxycarbonyl, methyldiethylamino groups, and bromine as the substituents in the resorcinol ring and methyl or phenyl substituents in the macro ring were synthesized. The absorption, excitation, phosphorescence, and luminescence spectra of these complexes were studied. The positions of triplet levels of the ligands were measured and the values of relative quantum yields for the complexes were calculated. The paths of ligand–lanthanide energy transfer are discussed.     

Luminescence of Ytterbium and Neodymium in Complexes with Bis-Macrocyclic Ligands

We have studied the spectral-luminescent characteristics of ytterbium and neodymium ions in complexes with new polydentate bis-crown-ether and bis-azacyclic ligands both of whose parts are bound by 2,9-substituted 1,10-phenanthroline. The relationship between the intensity, rare-earth ion luminescence lifetime, and the composition of the coordination sphere of the complexes is established. Using the considered compounds as an example, we show the advantage of the joint influence of screening of the central ion from the effect of high-frequency O–H- and C–H vibrations of the solvent molecules and of the photoantenna effect in improvement of the luminescent characteristics of lanthanides.     

稀土铕-芳香羧酸-邻菲罗啉三元有机配合物的合成、表征及发光性能

分别以4种芳香羧酸—对甲基苯甲酸(PMBA)、对氯苯甲酸(PCBA)、对溴苯甲酸(PBr BA)、对氨基苯甲酸(PABA)—作为第一配体,邻菲罗啉(phen)为第二配体,采用溶剂热法合成了4种稀土铕离子(Eu3+)的三元有机配合物。通过元素分析、红外光谱、热重分析等手段确定配合物的化学结构,结果表明,4种配合物的组成可表示为Eu L3phen·H2O(L=PMBA、PCBA、PBr BA、PABA),芳香羧酸配体和邻菲罗啉均与稀土Eu3+配位;铕配合物在318℃以上才开始出现明显失重,表明其具有良好的热稳定性。研究了4种芳香羧酸配体对紫外光的吸收性能。通过荧光光谱研究了配合物的发光性能,4种配合物均发出Eu3+的特征荧光,5D0→7F2电偶极跃迁发射峰强度顺序为:Eu(PBr BA)3phen·H2OEu(PMBA)3phen·H2OEu(PCBA)3phen·H2OEu(PABA)3phen·H2O;其国际照明委员会(CIE)色坐标均落在红光区域,能发出纯正的红光。     

有机量子阱发光的研究

有机量子阱具有优异的光电性能,在光电子器件中有广泛的应用.论述了如何证明有机量子阱的存在及其国内外研究现状,介绍了有机量子阱在有机电致发光中的应用以及存在的问题,重点是如何利用有机量子阱提高发光性能,并指出了今后的研究方向.     

不同发光染料的顶发射有机电致发光器件的研制

通过设计合理的微腔结构,制备了基于绿光染料C545t、黄光染料Rubrene、红光染料DCJTB的3种顶发射有机电致发光器件。研究了不同发光染料对顶发射器件的光谱的影响。研究表明,微腔结构对光谱具有窄化作用。绿光、黄光器件的发光峰波长并未随视角增大而明显变化,体现出良好的光谱角度性,而红光器件却出现了明显的光谱蓝移现象。绿光器件的最大功率效率为8.7 lm/W,当电流密度为45 m A/cm2时,亮度能达到7 205 cd/m2;黄光器件的电流效率最大值为11.5 cd/A,当电流密度为48 m A/cm2时,亮度可达到3 770 cd/m2;红光器件的电流效率最大能达到3.54 cd/A,当电流密度为50 m A/cm2时,可获得1 358 cd/m2的亮度。采用合适的发光材料以及合适的器件结构,不仅可以提高顶发射器件的色纯度及发光效率,还可以改善器件发光光谱的角度依赖性。     

铥配合物的红外有机电致发光

合成了两种三价铥配合物,并将其制成双层结构器件。首次得到了直流低压驱动下,来自铥离子＾３Ｈ４→＾３Ｈ６电子跃迁红外（ＩＲ）发光。     

不同有机碱对铕-2-羟基喹啉-4-羧酸配合物发光性能的影响

分别在有机碱三乙胺、三丙胺和三丁胺的作用下,使用2-羟基喹啉-4-羧酸(H2hqc)与EuCl3·6H2O反应制备了3种配合物Eu(Hhqc)3(TEL)、Eu(Hhqc)3(TPL)和Eu(Hhqc)3(TBL)。通过元素分析、热重分析、摩尔电导率、紫外光谱、荧光光谱、荧光寿命和量子产率等对配合物进行了表征。所有配合物均在580,592,613,654,702 nm附近产生5条谱带,为Eu3+的特征发射,归属为5D0→7FJ(J=0,1,2,3,4)能级间的跃迁,荧光寿命分别为2.22,3.29,3.31 ms,量子产率分别为0.011,0.019,0.028。随着有机胺碳链长度的增加,配合物的荧光强度依次增大,表明有机碱参与了配合物的分子组成。     

Ir配合物染料调节有机发光二极管发光特性

为了研究有机发光二极管(OLED)中发光特性与材料能带结构的关系,把不同的Ir配合物染料掺杂到结构相同的OLED器件中。OLED结构为ITO/NPB/CBP∶染料/TPBi/Mg∶Ag/Ag,染料分别为Ir(MDQ)2(acac)、Ir(ppy)3和Firpic。实验表明,这3种染料对应的掺杂器件分别发红光、绿光和蓝光。3个器件的阈值电压基本一致((6为了研究有机发光二极管(OLED)中发光特性与材料能带结构的关系,把不同的Ir配合物染料掺杂到结构相同的OLED器件中。OLED结构为ITO/NPB/CBP:染料/TPBi/Mg:Ag/Ag,染料分别为Ir(MDQ)₂(acac)、Ir(ppy)₃和Firpic。实验表明,这3种染料对应的掺杂器件分别发红光、绿光和蓝光。3个器件的阈值电压基本一致((6±0.1) V),但是,在100 cd/m²亮度下,绿光器件外量子效率最高(7.64%),蓝光器件外量子效率(5.65%)与绿光相近,红光器件外量子效率最低(2.75%)。分析认为,由于染料的掺杂浓度低,器件结构和载流子传输特性变化小,因而掺杂对阈值电压影响小;CBP与掺杂染料间存在能量转移,红色染料能级差小,非辐射跃迁几率大,发光效率最低;相比于绿光,蓝色染料能级差大,跃迁几率小,因此发光效率比绿光低。实验还发现,染料的发光波长与其能级差相比有红移现象,分析认为,这是由激发态能量振动弛豫和系间窜越过程形成的。     

Multi-Photon Sensitized Excitation of Near Infrared Emitting Lanthanides

Near infrared (NIR) multi-photon excitation of the NIR-emitting lanthanides neodymium (Nd³⁺) and ytterbium (Yb³⁺) sensitized by a fluorescein-linked chelator was demonstrated. Because tissues display minimal absorbance near the excitation wavelength of 800 nm, and because the lanthanides display long decay times, these results suggest the use of Nd³⁺ and Yb³⁺ as luminescent probes in tissues with multi-photon excitation.     

Luminescence of Leuco-Thiazine Dyes

Details of the novel luminescence of the leuco forms of the thiazine dyes, methylene blue and thionine, are reported, including their emission maxima, quantum yields and lifetimes of the luminescence. Other work shows that this luminescence is independent of reducing agent type and solution pH and is a common feature of most thiazine dyes.     

2018年11期 电子期刊

红外长余辉技术在生物成像探测及夜视保密探测等领域有着广阔的应用前景。本文结合该领域近期的一些进展,对红外长余辉的定义、发光离子的选择、发光动力学过程以及红外长余辉激发谱学技术等几方面进行了简要阐述。在阐述过程中也着重指出了红外长余辉领域今后的几个可能学术研究方向。     

有机材料激子发光的温度特性

基于实验和理论模拟研究了12~320 K温度范围内八羟基喹啉铝[tris-(8-hydroxyquinoline)aluminum,Alq]和一种高效红光染料甲基2叔丁基6(1,1,7,7四甲基久咯呢定基9烯基)4H 1吡喃[4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran,DCJTB]的光致发光(photoluminescence,PL)随温度的变化,提出三种不同电荷分离程度的激子参与的Alq的稳态光致发光过程,通过拟合参量得到了三种激子的能量差值和辐射复合几率之比,观察并解释了DCJTB发光光谱从200 K以下到室温的升温过程中发生的蓝移。认为变温光致发光有可能用于评估材料的发光和导电性能,比较并讨论了有机和无机发光材料激子发光的温度特性,认为低温下小分子发光材料倾向于分子态,随温度升高逐渐向半导体态转变,Alq在150~190K之间开始发生这种转变,而DCJTB则从300~320 K开始。     

Luminescence of Ytterbium in Complexes with Cryptands Containing Bipyridine and Biisoquinoline Fragments

Some characteristics of 4fluminescence of an ytterbium ion with cryptands containing bipyridine and biisoquinoline fragments have been studied for the first time. The relationship has been established between the changes in these characteristics and the structure of a macrocyclic ligand in H₂O and D₂O at 295 and 77 K. It is shown that the highest intensities and lifetimes of 4fluminescence are observed in those complexes where a lanthanide ion is most effectively protected against water molecules.     

铒配合物的红外有机电致发光

研究了三价饵离子配合物在近红外区段的电致及光致发光特性。采用双层电致发光器件获得了饵离子位于1530nm的光发射,并通过改进后的三层结构器件的红外发射明显提高,首次获得了Er(DBM)3bath在977nm和1530nm的发射。总结不同电流密度下的系发射光谱强度变化规律,发现随电流密度增大,虽然光谱强度的增长呈近似线性,但相对效率却在急剧下降,对这一现象做了这初步讨论。器件在可见区有发光,其来源归结为激基复合物的发射。     

分子型含铽离子-磺基水杨酸配合物无机/有机光功能杂化材料的设计与表征

通过对5-磺基水杨酸进行化学修饰并引入偶联基团,同Tb³⁺配位后与正硅酸乙酯水解缩聚来制备以强化学键结合的光功能杂化材料。利用紫外光谱、核磁共振等来表征中间体和材料的结构。荧光数据表明:材料表现出Tb³⁺的特征光谱,并具有良好的发光性能。     

铒有机配合物的合成、表征与近红外发光性能研究

合成了乙酰基丙酮(AcAc)和二苯甲酰基甲烷(DBM)的水合二元铒配合物以及乙酰基丙酮、二苯甲酰基甲烷和三氟乙酰基丙酮(TFA)分别与1,10-邻菲罗啉(Phen)的三元铒配合物,并经元素分析确认;表征了配合物的紫外-可见吸收光谱和红外吸收光谱;探讨了铒配合物的近红外发光性能,并对不同配体对发光性能的影响进行分析比较。结果表明Er(AcAc)₃Phen三元配合物是所研究的几种配合物中近红外发光性能最优的。     

稀土-PAN配合物的近红外发光研究

金属指示剂1－（2－吡啶偶氰）－2－萘酚（PAN）对Ln^3 (Ln^3 -Yb^3 ,Nd^3 和Er^3 )的近红外发光有不同的敏化作用，不论在固体还是在溶液中，PAN分子都可显著地敏化Yb^3 离子的发光，对Er^3 离子的发光也有一定的敏化作用，但不能敏化Nd^3 离子的发光，溶剂的种类对配合物溶液的近红外发光强度有非常明显的影响，根据配体三重态能级与Ln^3 的发射能级匹配的原理和浓度猝灭效应，对不同条件下Ln-PAN配合物的近红外发光行为进行了解释。     

分子发光法研究空间位阻效应对包络物形成的影响

利用分子发光法研究了正丁醇(n-butanol,n-Bu)和苯酚(phenol,ph)存在下空间位阻效应对β-环糊精(Cyclodextrin,β-CD)和溴代萘(Bromonaphthalene,BrN)包络物形成的影响。在各自最佳实验条件下,2-BrN/β-CD/n-Bu/ph体系的室温磷光(RTP)强度不及1-BrN/β-CD/n-Bu/ph体系的三分之一;而其荧光发射光谱较1-BrN/β-CD/n-Bu/ph发射光谱红移5～10 nm,表明BrN中溴的空间位置对包络物的形成有显著的影响。两四元体系包络常数(K_f)的测定结果也进一步说明这一点。据此,讨论了上述包络物的形成机理。     

Fluorescent Dyes in Sol-Gel Glasses

We review the sol-gel technology and the methods by which fluorescent dyes can be incorporated into inorganic glasses and organic-inorganic composites. The performance of the dyes in solar concentrators, tunable lasers, and active waveguides is presented.     

Enhancement of Luminescence in the Photolysis Of Eu(III) Poly(Acrylic Acid-co-Butyl Methacrylate) Complexes

The fluorescent and photochemical properties of Eu (III) with copolymers of acrylic acid and butyl methacrylate were investigated. It was found that photochemical behavior of Eu³⁺ complexes with copolymers is essentially different from those of Eu³ with polyacrylic acid - in the former Eu³ luminescence intensity during photolysis noticeably enhances rather than reduces. It has been found that the presence of steric hindrances and coordinatively unsaturated structures in the initial complexes with copolymer and peculiarities of the photodecomposition of macromolecular ligand favors the enhancement of the luminescence during the photolysis