Effect of Metal Cation on Absorption and Fluorescence Spectra of Metal Complexes of 8-Hydroxyquinoline∗

8-Hydroxyquinoline complexes of Na(I), Ca(II), Mg(II), Zn(II), Mn(II), Cu(II), Al(III), In(III) and La(III) are synthesized. Photoluminescence and UV-vis absorption spectra of them are reported. Except complexes of Cu(II), and Mn(II), these complexes show photoluminescence. With the increase of polarization force of metal cation, their photoluminescence peaks reveal red-shift and two broad absorption bands in UV-vis absorption spectra appear split and red-shift.

     

Tris (8-Hydroxyquinoline) Aluminium Nanostructure Film and Its Fluorescence Properties

Tris (8-hydroxyquinoline) aluminium (Alq3) nano-structured films are fabricated by the gas evaporation method, and their fluorescent properties are investigated in detail. Compared with the conventional amorphous Alq3 films, the fluorescent efficiency of the nanostructure films is enhanced to a certain extent.     

5,6,11,12-四苯基四苯并掺杂8-羟基喹啉铝薄膜的荧光谱及发光机理

用高荧光染料的5，6，11，12－四苯基四苯并对8－羟基喹啉铝进行掺杂，测量其光致发光和电致发光谱。结果表明：在低掺杂时，主发光体是Alq，掺入的Rubrene作为客发光体只是在Alq带隙中引入了分立能级；随着掺入的Rubrene浓度增加，Rubrene成了主发光体，Alq变成了客发光体，出现了发光体的互换现象。由于Rubrene的吸收光谱与Alq的发射谱重叠较大，在光致发光中存在从Alq向Rubrene的能量传递和电荷转移过程，而电致发光则是由于Rubrene导带中电子浓度远大于注入到Alq导带中电子浓度，造成Rubrene导带电子与价带空穴复合的几率比Alq中的复合几率大得多，其EL主要是Rubrene的发光。     

高相对分子质量8-羟基喹啉锂聚合物的制备和性能

高分子电致发光显示器(PLED)是近几年来国际、国内的研究热点,取得了很大的进展,其中高分子化金属配合物是一类很有价值的功能材料。通过甲基丙烯酸甲酯(MMA)、苯乙烯(S)和含有8-羟基喹啉的单体共聚合成模板聚合物,再与氢氧化锂作用,实现了8-羟基喹啉锂配合物的高分子化,获得了一种能够溶解在普通的溶剂中的高相对分子质量的含喹啉锂配合物的发光聚合物,并利用元素分析、¹H-NMR、FTIR、UV、PL光谱、DSC、TGA、GPC等方法对其结构和性能作了表征。紫外吸收和光致发光(PL)光谱说明合成共聚物的发光来自于Liq基团,引入的可聚合的链段以及共聚物中的甲基丙烯酸甲酯或苯乙烯链段,并没有影响发光波长的改变。亲核溶剂改变8-羟基喹啉金属配合物分子结构,使共聚物光谱明显红移20nm左右。     

Effect of Gamma Radiation on the IR Spectra of Some Divalent and Trivalent 8-Hydroxyquinoline Complexes

The I R spectra of ten elements chelated with 8-hydroxyquinoline were measured before and after gamma irradiation with different doses (7–518 Mrd) and discussed. It was found that the rate of decrease, K, of the absorbancy of M—O and (C—O)-M stretching vibration bands depends on the chelated cation. Moreover, the Cu 8-hydroxyquinoline complex is suggested as gamma dosimeter for doses ranging from 4.8 to 160 Mrd.     

Spectral-Luminescent Properties of Substituted Tetraazachlorin and of Its Zinc Complex

The spectral, energy, kinetic, and polarization characteristics of fluorescence of di(tert-butylbenzo)barrelene-substituted tetraazachlorin and of its zinc complex in solutions are measured. The results are compared with similar data for tetraazaporphin and unsubstituted chlorin. Quenching of the fluorescence of the tetraazachlorins under investigation is noted.     

7-羟基喹啉在二甲基亚砜中的荧光光谱

7-羟基喹啉(7-HQ)是一种具有激发态质子转移(ESPT)效应的有机分子。它溶于乙醇溶剂中,在紫外光的激励下,将发生ESPT反应,荧光光谱出现2个荧光带。7-HQ溶于二甲基亚砜(DMS)溶剂中,则不能发生ESPT反应,其荧光光谱只出现单一荧光带。但样品被强紫外光照射后,其荧光光谱也出现2个荧光带。文章首次报道了这一现象,并通过对7-HQ的乙醇、二甲基亚砜和二甲基甲酰胺溶液的吸收光谱和荧光光谱的研究,探讨产生这一现象的机理。认为7-HQ溶于DMS中被强紫外光照射后荧光光谱的变化是由于DMS被光解并生成水而使7-HQ发生ESPT反应的结果。     

The Infrared and 1H-NMR Spectra of 8-Hydroxyquinoline Adducts of 8-Hydroxyquinoline Complexes of Dioxouranium(VI), Thorium(IV) and Scandium(III)

The ¹H-nmr and infrared spectra of the complexes [M(ox)_n(Hox)] where M = UO₂ (n = 2), Th (n = 4) or Sc (n = 3) and Hox = 8-hydroxyquinoline are discussed. The nmr spectra of the adducts are uninformative with respect to the bonding and structure of these molecules since they dissociate in solution. The solid state ir spectra show that the adducted molecule of 8-hydroxyquinoline is bound to the metal through the phenolic oxygen, the proton forming an intramolecular hydrogen bond between the nitrogen atom of the adducted molecule and the oxygen atom of a neighbouring chelate ring. The mid-and far-ir spectra are reported for the first time and assignments for the δN-H, νM-O and νM-N modes have been made.     

8-羟基喹啉螯合Cu~(2+)的密度泛函理论研究

为揭示8-羟基喹啉树脂对Cu~(2+)高选择性吸附的本质原因,采用密度泛函B3LYP方法系统研究8-羟基喹啉与Cu~(2+)配位作用方式与作用特点.能量计算结果表明去质子的8-羟基喹啉阴离子与Cu~(2+)作用最强,相互作用能最高,其次是反式8-羟基喹啉,而顺式配体作用最弱;同时,金属离子与一个配体配位所得产物LCu~(2+)与配体配位能力显著降低.轨道分析表明金属离子主要以3d轨道与配体的2p轨道重叠,且以σ成键作用为主.静电势计算结果显示去质子的8-羟基喹啉阴离子静电势最负,导致配位能力明显高于中性配体;且金属离子与配体配位后,正的静电势显著降低,由此导致与配体配位能力减弱.     

Structure and Properties of Nanocrystalline Zinc Films

We have developed a unique processing technique to fabricate Zinc (Zn) nanocomposites with controlled microstructures. In this method, pulsed laser deposition of Zn in conjunction with a few monolayers of tungsten (W) is used to control the grain size of nanocrystalline composites. The grain size of Zn was controlled by the amount of Zn and the substrate temperature. The Zn islands of lower surface energy nucleate on W-layer of high surface energy, which is also insoluble in Zn resulting in lower interfacial energy. Using this approach, we have fabricated nanocomposites of grain sizes ranging from 30nm down to 6nm. The hardness of these nanocrystalline films increases with the decrease in grain size, following approximately Hall–Petch relationship. The most interesting observation is the decrease in hardness below a critical size, which is explained on the basis of grain boundary deformation/sliding. The role of W in grain boundary deformation is of particular interest in strengthening and stabilizing the nanocrystalline composites. The potential of this technique to attain even lower grain sizes is discussed.     

铕-苯甲酸-邻菲咯啉掺杂配合物体系的合成与荧光性能研究

合成了Eu_1-xLn_x(BA)₃ Phen(Ln： Gd,La,Y;BA： 苯甲酸;Phen： 1,10-邻菲咯啉)系列固体粉末配合物。红外光谱的研究表明该系列配合物具有相似的结构;荧光光谱表明该类配合物均能发出强的铕离子的特征荧光,并且掺杂元素能增强配合物的发光性能,起到共发荧光作用。     

含混杂配体的Zn配合物的分子振动光谱研究

ＭＳ＾２－４（Ｍ＝Ｍｏ、Ｗ、Ｖ等）阴离子由于灵活多样的配位方式可形成特殊的构造单元而被广泛应用于分子设计中,本文对含有ＭＳ＾２－４及１,１０－ｐｈｅｎａｎｔｈｒｏｌｉｎｅ的混配金属配合物Ｚｎ（ｐｈｅｎ）２ＷＳ４和Ｚｎ（ｐｈｅｎ）２ＭｏＳ４的晶体进行红外光谱和拉曼光谱的研究并讨论了谱学与结构的关系。     

8-羟基喹啉-山梨酸稀土配合物与鲱鱼精DNA相互作用的光谱研究

合成了以山梨酸(SA)和8-羟基喹啉(Hq)为配体的Sm(Ⅲ)、Eu(Ⅲ)为中心的三元稀土配合物,研究了配合物与DNA之间的作用机制。采用红外光谱、紫外-可见吸收光谱、差热热重、元素分析和摩尔电导等方法,确定了配合物的化学组成,采用光谱法探讨了配合物与鲱鱼精DNA的作用机制。结果表明:配合物的化学组成为Sm(Hq)(SA)2和Eu(Hq)(SA)2,其最大吸收峰在加入DNA后发生减色和红移,中性红(NR)使配合物-DNA体系的吸收发生减色,伴有等色点出现。配合物的加入导致NR-DNA体系的吸收峰强度和位置发生变化。计算求得Eu(Hq)(SA)2和Sm(Hq)(SA)2分别与DNA的结合位点数为5,在20℃下,Sm(Hq)(SA)2、Eu(Hq)(SA)2与DNA的结合常数分别是2.04×104L/mol和1.09×104L/mol。2种稀土配合物都能不同程度地猝灭NR-DNA体系的荧光,表明2种稀土配合物对DNA都有较强的嵌插作用且能自发进行,结合能力为Sm(Hq)(SA)2Eu(Hq)(SA)2。     

稀土荧光特性与温度关系

为研究稀土荧光特性与温度关系,从典型稀土材料的能级结构出发,根据激发态多能级间的玻尔兹曼热平衡分布理论,对激发态能级的粒子数分布情况与温度关系进行研究.发现随着温度的上升稀土发光荧光寿命变短,激发态高能级辐射荧光比例增大;而荧光强度由于受到非辐射跃迁系数和能量传递效率的双重影响将会呈现先上升后下降的变化.以钒磷酸钇铕Y(P,V)O4∶Eu3+荧光粉材料为例进行实验研究,测量了95K到510K温度范围内Y(P,V)O4∶Eu3+荧光材料在395nm紫外光激励下所发荧光的荧光寿命、荧光强度和荧光分支比随温度的变化规律,实验结果与理论相符合.     

取代金属(铁、锰、钴、铜、锌)卟啉的光谱分析

对系列取代金属(铁、锰、钴、铜、锌)卟啉化合物的紫外光谱、红外光谱、远红外光谱进行了详尽的测试和分析,揭示了不同结构金属卟啉的光谱规律,从理论上分析了形成光谱规律的原因。针对目前氯化铁卟啉轴向Fe—Cl键远红外表征的报道结果不一致性,采用理论分析与实验测定相结合的方法,探索了氯化铁卟啉中Fe—Cl键远红外吸收规律。研究结果表明：Fe—Cl键的振动吸收频率不是固定不变的,而是与卟啉环的结构有关,且和Fe—Cl的键长呈线性关系。     

基于萘酰腙类锌离子增强型荧光探针的合成及光谱性能

设计合成了一种简单的酰腙类结构的增强型荧光探针HM,实现了对锌离子（Zn²⁺）的高选择性识别。运用ESI-MS质谱、荧光光谱和紫外-可见光谱等手段研究了探针HM对Zn²⁺的识别过程。紫外光谱测试表明,当向探针HM中加入Zn²⁺后,386 nm处的吸收峰逐渐减弱,在420 nm处出现了新的吸收峰,并且强度逐渐增大,直至达到平衡,等吸收点为396 nm。荧光光谱分析表明,探针HM能够高选择性地识别Zn²⁺。在发射波长510 nm处的荧光增强2.5倍,最低检出限为1.0×10^-5 mol/L、量子产率为0.02。该识别过程为PET（光诱导电子转移机理）和CHEF（螯合荧光增强机理）共同作用的结果。通过电喷雾质谱和Job's plot实验证明探针HM与Zn²⁺以1：1配位,平衡常数（K）达到4.05×10⁶ L·mol^-1。     

光谱法研究3H-吲哚探针分子与牛血清蛋白的相互作用

以荧光技术研究一种新型探针分子--2-(对-氨基苯基)-3,3-二甲基-3H-吲哚(A)与牛血清蛋白(BSA)结合反应的特征,测定了结合常数(K=1.82×105L/mol).依据Foester非辐射能量转移理论,确定了授体-受体间的结合距离(r=2.34nm)和能量转移效率,采用同步荧光技术考察了A对BSA构象的影响.     

RE(POA)3phen配合物的合成、表征及荧光性能

合成了以稀土离子Sm³⁺、Eu³⁺、Tb³⁺、Dy³⁺及Tb³⁺为发光中心,以苯氧乙酸(HPOA)和邻菲罗啉(phen)为配体,掺杂La³⁺、Gd³⁺、 Y³⁺的7种稀土配合物, 对配合物进行了C、H、N元素分析、稀土络合滴定、红外光谱、紫外光谱和发光光谱的研究。结果表明配合物的组成分别为SmL₃L'·1/2H₂O,EuL₃L'·1/2H₂O,TbL₃L'· 1/2H₂O,DyL₃L'·1/2H₂O,掺杂配合物组成分别为Tb_0.5Gd_0.5L₃L'·1/2H₂O,Tb_0.5Y_0.5L₃L'·1/2H₂O,Tb_0.5La_0.5L₃L'·1/2H₂O(L=C₆H₅OCH₂COO^-, L'=phen)。配合物中的稀土离子与苯氧乙酸中羧基的一个氧原子和苯氧基的氧原子配位,与邻菲罗啉中的两个氮原子配位成键;荧光光谱表明,铽三元配合物的发射强度要远大于其它三元配合物的发光强度,掺杂发光惰性稀土离子La³⁺、Gd³⁺、Y³⁺的铽配合物中,Y³⁺掺杂配合物的发光强度有所增强。     

Specific Fluorescence Properties and Picosecond Transient Absorption of 8-Azasteroids

The specific fluorescence properties as well as picosecond transient absorption features have been studied for two 8-azasteroids. It is shown that at various excitation wavelengths the essentially different final excited electronic states are realized. Because of the multicenter character of 8-azasteroids the spectroscopic data obtained may be analyzed on a basis of the mesomeric tautomerism model taking into account the dynamic combination of cis- and trans-configurations. The dependence of fluorescence spectral characteristics on the solvent nature is a manifestation of intermolecular H-bond interactions.     

2-(4-氟代苯甲酰基)苯甲酸-铕配合物的合成、结构表征及荧光性能的研究

以硝酸铕、2-(4-氟代苯甲酰基)苯甲酸(HL)、1,10-菲咯啉(Phen)和三苯基氧膦(TPPO)合成了EuL₃(H₂O)₆,EuL₃Phen(H₂O)₄和EuL₃(TPPO)(H₂O)₅三种固态配合物。用元素分析、红外光谱、核磁共振氢谱对配合物进行了组分确定和结构表征。IR表明,2-(4-氟代苯甲酰基)苯甲酸与Eu3+形成配合物后,位于1 692 cm-1处羧基的ν_CO峰消失,2 500～3 200 cm-1处羧基的ν_O—H峰也消失,出现了羧酸盐特有的反对称伸缩振动吸收峰(ν_as(CO-₂))和对称伸缩振动吸收峰(ν_s(CO-₂)),且Δν(ν_as(CO-₂)-ν_s(CO-₂))与钠盐的Δν相近,说明羧酸根与Eu3+以对称双齿桥式配位。在1H NMR中,形成配合物后第一配体苯环上的质子峰变为宽峰且移向高场,Phen和TPPO中质子化学位移移向低场。室温下测定了配合物的荧光激发光谱和发射光谱,激发光谱表明配合物EuL₃(H₂O)₆,EuL₃Phen(H₂O)₄和EuL₃(TPPO)(H₂O)₅的最佳激发波长分别为353.0,355.0和357.0 nm;发射光谱均显示Eu3+离子的特征发射光谱,且表明Phen对Eu3+离子的荧光发射有明显增强作用。