铽配合物[Tb(m-MBA)3phen]2·2H2O的有机电致发光

将稀土铽配合物[Tb(m MBA)3phen]2·2H2O作为发光材料应用于有机电致发光。把铽配合物掺杂在PVK中经甩膜制得发光层,并分别用AlQ和PBD作为电子传输层制作了两类有机电致发光器件。器件1:ITO PVK:[Tb(m MBA)3phen]2·2H2O PBD LiF Al;器件2:ITO PVK:[Tb(m MBA)3phen]2·2H2O AlQ LiF Al,研究了两种器件的电致发光性能,并通过选择AlQ的厚度得到了发光性能较好的用AlQ作为电子传输材料的器件,其最大亮度在20V时达到140cd·m-2。     

稀土配合物Tb(p-MBA)3phen的有机电致发光

合成了一种新型的稀土铽配合物材料Tb(p-MBA)3phen,把它作为发光材料应用于有机电致发光中.把铽配合物掺杂在导电聚合物PVK中采用旋涂法制得发光层,并利用AlQ作为电子传输层制作了单层、双层有机电致发光器件:器件1(ITO/PVK):Tb(p-MBA)3phen/Al;器件2(ITO/PVK):Tb(p-MBA)3phen/AlQ/LiF/Al,得到了纯正的、明亮的Tb3 离子的绿光发射,4个特征峰分别对应着能级5D4到7Fj(j=6,5,4,3)的跃迁,而PVK的发光完全被抑制.研究了两种器件的电致发光性能,并通过选择AlQ的厚度得到了发光性能较好的器件,其最大亮度在20 V时达到152 cd·m-2.     

Eu(BSA)3phen与PVK共混体系的光致和电致发光特性的研究

合成了一类新型的以苯甲酰水杨酸(benzoyl salicylic acid,BSA)为第一配体,邻菲罗啉(1,10-phenanthroline,phen)为第二配体的稀土配合物Eu(BSA)3phen,将导电高分子材料PVK引入到配合物中,制成了结构为ITO/PVK:RE配合物/LiF/Al的电致发光器件.通过测量电致发光和光致发光光谱,发现PVK:RE配合物混合体系存在着能量传递,并对Eu(BSA)3phen与PVK共混体系的光致发光和电致发光机制进行了分析.同时比较了几种不同PVK掺杂浓度对于器件性能的影响.     

稀土铽配合物TbY(m-MBA)6(phen)2·2H2O的有机电致发光

合成了两种新型稀土配合物[Tb(m-MBA)3phen]2·2H2O和TbY(m-MBA)6(phen)2·2H2O, 将其掺杂到导电聚合物PVK中用于有机电致发光器件的发光层, 这样改善了配合物的成膜特性和导电性质. 用这种搀杂体系分别制作了单层发光器件和以AlQ为电子传输层的双层器件. 研究了这些单、双层器件的电致发光性能, 对比了以[Tb(m-MBA)3phen]2·2H2O为发光层的双层器件和以TbY(m-MBA)6(phen)2·2H2O为发光层的器件, 发现后者效率更高, 为0.88 cd·A-1, 其最大亮度为123 cd·m-2.     

苯甲酰水杨酸铽与PVK混合体系的发光特性

合成了一类以苯甲酰水杨酸（benzoyl salicylic acid,BSA)为第一配体，邻菲罗啉（1,10-phenanthroline,Phen)为第二配体的稀土铽配合物，将导电高分子材料PVK引入到配合物中，制成了结构为ITO／PVK：Tb(BSA)3phen/PBD/Alq/LiF/Al电致发光器件，并对该配合物的吸收特性及电致发光和光致发光性能进行了研究，实验数据表明在PVK与Tb(BSA)3phen之间存在着Forster能量传递，该配合物具有很好的光致发光和电致发光性能。本文同时比较了几种不同PVK掺杂浓度对于器件性能的影响。     

铽配合物Tb(o-BBA)3(phen)有机电致发光研究

合成了一种新的稀土配合物邻苯甲酰苯甲酸-1，10-菲罗啉-铽（Tb（o-DDA）3（phen））并用于有机电致发光。研究了Tb（o-DDA）3（phen）与PVK混合薄膜的光敛发光特性，找出了PVK：Tb的最佳比例为3：1。制备了结构为ITO／PVK：Tb／Al的单层电致发光器件，得到了铽离子的特征光谱，其电流-电压特性（I-V）在一定电压范围内符合空间电荷限制电流机制。研究结果表明稀土铽配合物Tb（o-BBA）3（phert）掺杂PVK体系的光致发光是源于PVK到Tb配合物的能量传递及稀土Tb配合物的直接激发两种作用机制，而电致发光以载流子俘获为主。     

共掺杂稀土配合物Tb0.5Eu0.5(asprin)3phen电致发光的研究

合成了共掺杂稀土配合物Tb0.5Eu0.5(asprin)3phen，将其掺杂到导电聚合物PVK中，制成结构为ITO／PVK：RE配合物／PBD／Al的电致发光器件，与PVK：Eu(asprin)3phen体系为发光层的相同结构的器件相比，我们发现铽离子的引入能猝灭PVK的发光，增强铕的发光，而Tb3 本身的发光很弱，几乎看不到，说明Pb3 在其中起到能量的中间传递作用，促进了PVK到Eu^3 的能量传递，本文就器件的发光特性及掺杂体系的能量传递进行了初步讨论。     

一类新型稀土配合物的合成与发光特性研究

合成了一类新型稀土配合物Eu(asprin)3phen和Tb(asprin)3phen,并将其掺杂到导电聚合物PVK中,制成结构了为ITO／PVK：RE配合物／LiF/Al的电致发光器件。很明显,在相同掺杂比例下,前者的电致发光中PVK发射所占比例较大,而后者的电致发光中PVK的发射几乎全部被覆盖掉了,进一步研究发现它们的光致发光中也有同样现象存在,这表明具有同等配体的此类铕、铽配合物的特性存在很大差别,并对这一差别作了初步讨论。     

Sm(DBM)3phen的光致发光和电致发光性质

制备了一系列基于配合物Sm(DBM)3phen的电致发光器件. 研究了其光致发光(PL)和电致发光(EL)性质, 实验结果表明, Sm(DBM)3phen具有良好的电子注入和传输性能以及电致发光性能. 器件ITO/TPD(50 nm)/Sm(DBM)3phen(50 nm)/Alq3(30 nm)/LiF(1.0 nm)/Al的最大亮度和最大效率分别为150 cd/m2和0.72 cd/A, 器件表现为纯Sm3+离子的发光.     

稀土铽配合物TbY(m-MOBA)6(phen)2·2H2O的有机电致发光单层器件的研究

将新型稀土配合物TbY(m-MOBA)6(phen)2·2H2O掺杂到导电聚合物PVK中改善了铽配合物的成膜特性和导电性质.用此掺杂体系制作了单层发光器件,发现掺杂浓度为1:5,甩膜转速为1000r·min-1时器件的发光效果最好,起亮电压为9 V,最大亮度在17 V时达到15.7cd·m-2.对比[Tb(m-MOBA)3phen]2·2H2O的单层器件的发光,说明Y3 的存在促进了PVK到Tb3 的能量传递.     

OH(3) (-) and O(2)H(5) (-) double Rydberg anions: predictions and comparisons with NH(4) (-) and N(2)H(7) (-)

A low barrier in the reaction pathway between the double Rydberg isomer of OH(3) (-) and a hydride-water complex indicates that the former species is more difficult to isolate and characterize through anion photoelectron spectroscopy than the well known double Rydberg anion (DRA), tetrahedral NH(4) (-). Electron propagator calculations of vertical electron detachment energies (VEDEs) and isosurface plots of the electron localization function disclose that the transition state's electronic structure more closely resembles that of the DRA than that of the hydride-water complex. Possible stabilization of the OH(3) (-) DRA through hydrogen bonding or ion-dipole interactions is examined through calculations on O(2)H(5) (-) species. Three O(2)H(5) (-) minima with H(-)(H(2)O)(2), hydrogen-bridged, and DRA-molecule structures resemble previously discovered N(2)H(7) (-) species and have well separated VEDEs that may be observable in anion photoelectron spectra.     

Mixed ligand titanium(IV) complexes. Chlorobis(dithiocarbamato)bis(methylsalicylato)titanium(IV) andbis(dithiocarbamato)bis(methylsalicylato)titanium(IV)

Summary Dichlorobis(methylsalicylato)titanium(IV) reacts with potassium or amine salts of dialkyl or diaryl dithiocarbamates in 11 and 12 molar ratios in anhydrous benzene (room temperature) or in boiling CH₂Cl₂ to yield mixed ligand complexes: (AcOC₆H₄O)₂ Ti(S₂CNR₂)Cl (1) and (AcOC₆H₄O)₂ Ti(S₂CNR₂)₂ (2), R=Et, n-Pr, n-Bu, cyclo-C₄H₈ and cyclo-C₅H₁₀. These compounds are moisture sensitive and highly soluble in polar solvents. Molecular weight measurement in conjunction with i.r.,¹H and¹³C n.m.r. spectral studies suggest coordination number 7 and 8 around titanium(IV) in (1) and (2) respectively.     

Bis(trifluoroacetyl) peroxide, CF(3)C(O)OOC(O)CF(3)

Pure, highly explosive CF(3)C(O)OOC(O)CF(3) is prepared for the first time by low-temperature reaction between CF(3)C(O)Cl and Na(2)O(2). At room temperature CF(3)C(O)OOC(O)CF(3) is stable for days in the liquid or gaseous state. The melting point is -37.5 degrees C, and the boiling point is extrapolated to 44 degrees C from the vapor pressure curve log p = -1875/T + 8.92 (p/mbar, T/K). Above room temperature the first-order unimolecular decay into C(2)F(6) + CO(2) occurs with an activation energy of 129 kJ mol(-1). CF(3)C(O)OOC(O)CF(3) is a clean source for CF(3) radicals as demonstrated by matrix-isolation experiments. The pure compound is characterized by NMR, vibrational, and UV spectroscopy. The geometric structure is determined by gas electron diffraction and quantum chemical calculations (HF, B3PW91, B3LYP, and MP2 with 6-31G basis sets). The molecule possesses syn-syn conformation (both C=O bonds synperiplanar to the O-O bond) with O-O = 1.426(10) A and dihedral angle phi(C-O-O-C) = 86.5(32) degrees. The density functional calculations reproduce the experimental structure very well.     

Syntheses and structures of the infinite chain compounds Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14)

The alkali metal/group 4 metal/polychalcogenides Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) have been synthesized by means of the reactive flux method at 823 or 873 K. Cs(4)Ti(3)Se(13) crystallizes in a new structure type in space group C(2)(2)-P2(1) with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) A, b = 32.468(2) A, c = 14.6747(8) A, beta = 100.008(1) degrees. Cs(4)Ti(3)Se(13) is composed of four independent one-dimensional [Ti(3)Se(13)(4-)] chains separated by Cs(+) cations. These chains adopt hexagonal closest packing along the [100] direction. The [Ti(3)Se(13)(4-)] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs(4)Ti(3)Se(13). The compounds Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) crystallize in the K(4)Ti(3)S(14) structure type with four formula units in space group C(2)(h)()(6)-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) A, b = 8.1169(5) A, c = 13.1992(8) A, beta = 112.835(1) degrees for Rb(4)Ti(3)S(14);a = 21.329(3) A, b = 8.415(1) A, c = 13.678(2) A, beta = 113.801(2) degrees for Cs(4)Ti(3)S(14); a = 21.643(2) A, b = 8.1848(8) A, c = 13.331(1) A, beta = 111.762(2) degrees for Rb(4)Hf(3)S(14); a = 22.605(7) A, b = 8.552(3) A, c = 13.880(4) A, beta = 110.919(9) degrees for Rb(4)Zr(3)Se(14); a = 22.826(5) A, b = 8.841(2) A, c = 14.278(3) A, beta = 111.456(4) degrees for Cs(4)Zr(3)Se(14); and a = 22.758(5) A, b = 8.844(2) A, c = 14.276(3) A, beta = 111.88(3) degrees for Cs(4)Hf(3)Se(14). These A(4)M(3)Q(14) compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed [M(3)Q(14)(4-)] chains that run in the [101] direction and are separated by A(+) cations. Each [M(3)Q(14)(4-)] chain is built from a [M(3)Q(14)] unit that consists of two MQ(7) pentagonal bipyramids or one distorted MQ(8) bicapped octahedron bonded together by edge- or face-sharing. Each [M(3)Q(14)] unit contains six Q(2)(2-) dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) A for S-S and 2.367(1)-2.391(2) A for Se-Se. The A(4)M(3)Q(14) compounds can be formulated as (A(+))(4)(M(4+))(3)(Q(2)(2-))(6)(Q(2-))(2).