光致发绿光有机玻璃材料的研究

在氮气保护下，将配体α-噻吩甲酰三氟丙酮（HTTA）引入三异丙氧基铽中合成了铽配合物，并与甲基丙烯酸甲酯通过本体聚合制备含铽有机玻璃材料，用红外光谱（IR）、动态机械热分析（DMTA）、荧光光谱（FS）对其进行表征。结果表明，所制备的含铽有机玻璃在最佳波长激发下能发射很强的Tb^3＋离子特征绿光。DMTA测试表明，材料的玻璃化转变温度Tg、粘流温度矗及储能模量E′均比纯有机玻璃有所提高。     

掺C60有机玻璃的吸收光谱研究

研究了Ｃ６０分别在有机玻璃（ＰＭＭＡ）和正己烷中的吸收光谱，发现Ｃ６０在有机玻璃中的吸收峰同在正己烷中相互对应，同时前者的吸收峰相对于后者峰宽变大，峰位产生红移，分析了产生这种现象的原因。     

阻燃有机玻璃研究进展

有机玻璃属于易燃材料,存在严重的火灾隐患,其阻燃配方设计需要同时对聚甲基丙烯酸甲酯进行耐热改性和阻燃设计,并兼顾热变形性和机械性能等方面.改善耐热性主要通过在聚甲基丙烯酸甲酯上增加链段刚性、主价交联和副价交联,从而减缓甲基丙烯酸甲酯的分解,减少阻燃配方设计时阻燃剂用量.为了设计高玻璃化转变温度的材料,提高阻燃有机玻璃的力学性能,应尽可能降低添加型和可聚合型磷酸酯类阻燃剂的用量,其中可聚合磷酸酯类阻燃剂是今后阻燃有机玻璃技术发展的重要方向.在透明度要求不高的领域,采用二氧化硅纳米粉、氧化锌纳米棒、磷酸铝和石墨烯片状纳米材料与阻燃剂复配也可以得到良好的阻燃效果.     

γ射线辐照对含钆有机玻璃性能的影响EI北大核心CSCD

以^(60)Co作为γ射线源,对不同Gd元素含量的含钆有机玻璃进行不同剂量的γ射线辐照。通过可见光吸收光谱仪、万能试验机、热重分析仪和电子顺磁共振波谱仪等仪器测定含钆有机玻璃在γ射线辐照前后的光学性能、力学性能、热性能和自由基的变化。结果表明,随着γ射线辐照剂量的增加,含钆有机玻璃发生辐照降解,产生大量自由基,导致材料发生变色发黄现象,冲击强度、弯曲强度以及热稳定性能均有下降的趋势。且Gd元素含量越高,辐照降解程度越大。     

有机玻璃雕刻过程中有害气体的3阶段预浓缩GC/MS分析

研究了3阶段预浓缩气相色谱-质谱法检测有机玻璃在雕刻过程中排放的有害气体的组成。研究结果表明,气体中含有12种以上的有机污染物。其中甲基丙烯酸甲酯、丙烯酸甲酯、苯、甲苯、苯乙烯等5种有毒有害物可以作为代表该行业特征的污染物加以监控。     

有机玻璃微液流化学芯片的研制及性能

研究了有机玻璃微液流化学芯片的制作工艺及其条件，优化了制片过程的条件，在5-15kgf压力、170-180℃保温20min条件下使用微细金属丝和玻璃阳膜压印管道，在15kgf压力、120℃保温15min键合，制作了单层二维及双层三维变向的微液流芯片。并在所制作的微芯片上观测了双流体混合状态，对LuminolKMnO4-Pb^2 化学发光体系进行了测试。     

关于一维波向有机玻璃透射声抗偶合的粘弹效应

用SHPB技术测定了20—60℃范围内,有机玻璃的应力-应变曲线。用标准线性固体粘弹模型讨论了有机玻璃log(t) 随时间近似线性衰减的特性,得到反映声抗偶合的参数κ与粘弹性常数b=Ε’/η’相一致的结论。由κ值对温度的依赖性讨论了有机玻璃声抗偶合的粘弹效应。     

丁达尔现象演示器

该演示器的特点是可利用室内的散射光线进行实验,不需要其它光源。制作方法选厚3—4mm的有机玻璃板按附图的尺寸裁好,锯边磨光,然后用有机玻璃粘结剂(有机玻璃碎屑溶于三氯甲烷配成5％溶液)进行粘结。粘合后,分别在左右二槽中贮水,如发现渗漏,必须用粘结剂修补。     

胺基邻菲咯啉-钌(Ⅱ)反应性荧光指示剂的合成与化学固定的研究

为减少荧光指示剂被水萃取流失,提高荧光膜的使用寿命,将5-氨基-邻菲咯啉与二(4,7-二苯基-邻菲咯啉)二氯化钌(Ⅱ)络合,合成带氨基的荧光指示剂[Ru(dpp)₂(phen-NH₂)]Cl₂,并经氨基键合到有机玻璃表面。以核磁、质谱、红外验证合成荧光指示剂的结构,研究键合条件对染色有机玻璃荧光发射的影响,监测荧光强度随水浸泡时间的变化。合成荧光指示剂的荧光发射峰值波长为570 nm,键合到有机玻璃后发射光谱红移20 nm,荧光强度受溶解氧影响,响应时间约为10 s,氧猝灭比达4。染色有机玻璃的荧光稳定性好,在50 ℃水中浸泡7个月,荧光强度下降小于1%。     

电解食盐水

一、实验原理(略)二、实验步骤1.自制多功能隔膜电解器:用有机玻璃板锯成大小适当的有机玻璃块,用砂纸磨平边缘,用三氯甲烷做粘合剂粘接起来制成三个部分。     

本体聚合制备Sm(OPr~i)(TTA)_2/PMMA光致发光材料

合成了(异丙氧基)二(α-噻吩甲酰三氟丙酮基)钐[Sm(OPri)(TTA)2]配合物,并通过本体聚合制备Sm(OPri)(TTA)2/PMMA光致发光材料,采用IR1、H-NMR、XRD、DMTA、FS、ESEM对其进行表征.结果表明,Sm-(OPri)(TTA)2/PMMA在396 nm波长激发下在562、598、644 nm处发射很强的Sm3+离子4G5/2→6H5/2,4G5/2→6H7/2,4G5/2→6H9/2跃迁的特征荧光,其发光强度与Sm(TTA)3/PMMA相当;其储能模量E′、玻璃化温度Tg和粘流温度Tf均比PMMA有所提高;Sm(OPri)3/PMMA形成类似交联结构聚合物,而Sm(OPri)(TTA)2/PMMA为线型无定型结构聚合物.     

New insights into the polymerization of methyl methacrylate initiated by rare-earth borohydride complexes: a combined experimental and computational approach

Polymerization of methyl methacrylate (MMA) initiated by the rare-earth borohydride complexes [Ln(BH(4))(3)(thf)(3)] (Ln=Nd, Sm) or [Sm(BH(4))(Cp*)(2)(thf)] (Cp*=eta-C(5)Me(5)) proceeds at ambient temperature to give rather syndiotactic poly(methyl methacrylate) (PMMA) with molar masses M(n) higher than expected and quite broad molar mass distributions, which is consistent with a poor initiation efficiency. The polymerization of MMA was investigated by performing density functional theory (DFT) calculations on an eta-C(5)H(5) model metallocene and showed that in the reaction of [Eu(BH(4))(Cp)(2)] with MMA the borate [Eu(Cp)(2){(OBH(3))(OMe)C=C(Me)(2)}] (e-2) complex, which forms via the enolate [Eu(Cp)(2){O(OMe)C=C(Me)(2)}] (e), is calculated to be exergonic and is the most likely of all of the possible products. This product is favored because the reaction that leads to the formation of carboxylate [Eu(Cp)(2){OOC-C(Me)(=CH(2))}] (f) is thermodynamically favorable, but kinetically disfavored, and both of the potential products from a Markovnikov [Eu(Cp)(2){O(OMe)C-CH(Me)(CH(2)BH(3))}] (g) or anti-Markovnikov [Eu(Cp)(2){O(OMe)C-C(Me(2))(BH(3))}] (h) hydroboration reaction are also kinetically inaccessible. Similar computational results were obtained for the reaction of [Eu(BH(4))(3)] and MMA with all of the products showing extra stabilization. The DFT calculations performed by using [Eu(Cp)(2)(H)] to model the mechanism previously reported for the polymerization of MMA initiated by [Sm(Cp*)(2)(H)](2) confirmed the favorable exergonic formation of the intermediate [Eu(Cp)(2){O(OMe)C=C(Me)(2)}] (e') as the kinetic product, this enolate species ultimately leads to the formation of PMMA as experimentally observed. Replacing H by BH(4) thus prevents the 1,4-addition of the [Eu(BH(4))(Cp)(2)] borohydride ligand to the first incoming MMA molecule and instead favors the formation of the borate complex e-2. This intermediate is the somewhat active species in the polymerization of MMA initiated by the borohydride precursors [Ln(BH(4))(3)(thf)(3)] or [Sm(BH(4))(Cp*)(2)(thf)].     

Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding

A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).     

甲基丙烯酸甲酯与稀土配合物单体的共聚合研究

稀土异丙醇盐与β 二酮、丙烯酸、１ ,１０ 邻菲罗啉或２ ,２′ 联吡啶反应,生成的稀土配合物单体与甲基丙烯酸甲酯共聚合得３２ 种稀土金属有机高分子．共聚物用元素分析、ＦＴ ＩＲ、１Ｈ ＮＭＲ、ＸＰＳ、ＵＶ、ＧＰＣ、ＤＴＡ、ＴＧ 等技术进行表征．     

Luminescence tuning of imidazole-based lanthanide(III) complexes [Ln = Sm, Eu, Gd, Tb, Dy

To tune the lanthanide luminescence in related molecular structures, we synthesized and characterized a series of lanthanide complexes with imidazole-based ligands: two tripodal ligands, tris{[2-{(1-methylimidazol-2-yl)methylidene}amino]ethyl}amine (Me(3)L), and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(3)L), and the dipodal ligand bis{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(2)L). The general formulas are [Ln(Me(3)L)(H(2)O)(2)](NO(3))(3)·3H(2)O (Ln = 3+ lanthanide ion: Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)), [Ln(H(3)L)(NO(3))](NO(3))(2)·MeOH (Ln(3+) = Sm (6), Eu (7), Gd (8), Tb (9), and Dy (10)), and [Ln(H(2)L)(NO(3))(2)(MeOH)](NO(3))·MeOH (Ln(3+) = Sm (11), Eu (12), Gd (13), Tb (14), and Dy (15)). Each lanthanide ion is 9-coordinate in the complexes with the Me(3)L and H(3)L ligands and 10-coordinate in the complexes with the H(2)L ligand, in which counter anion and solvent molecules are also coordinated. The complexes show a screw arrangement of ligands around the lanthanide ions, and their enantiomorphs form racemate crystals. Luminescence studies have been carried out on the solid and solution-state samples. The triplet energy levels of Me(3)L, H(3)L, and H(2)L are 21?000, 22?700, and 23?000 cm(-1), respectively, which were determined from the phosphorescence spectra of their Gd(3+) complexes. The Me(3)L ligand is an effective sensitizer for Sm(3+) and Eu(3+) ions. Efficient luminescence of Sm(3+), Eu(3+), Tb(3+), and Dy(3+) ions was observed in complexes with the H(3)L and H(2)L ligands. Ligand modification by changing imidazole groups alters their triplet energy, and results in different sensitizing ability towards lanthanide ions.     

Tuning the self-assembly and luminescence properties of lanthanide coordination polymers by ligand design

Two new structure-related tripodal ligands featuring salicylamide pendant arms, 1,3,5-tris{[(2'-furfurylaminoformyl)phenoxyl]methyl}-2,4,6-trimethylbenzene (L(I)) and 1,1,1-tris{[(2'-furfurylaminoformyl)phenoxyl]methyl}ethane (L(II)) have been designed and synthesized with the ultimate aim of self-assembling lanthanide polymers with interesting luminescent properties. Among two series of Ln(III) nitrate complexes (Ln = Pr, Nd, Sm, Eu, Gd, Tb or Dy) which have been characterized by elemental analyses, XRD, TGA and IR spectra, three new coordination polymers have been determined by X-ray diffraction analysis. The coordination polymer type {[Ln(NO(3))(3)(L(I))].nH(2)O}(n) possesses an unusual ladderlike double chain which can be further connected through pi-pi stacking interactions constructing a three-dimensional supramolecular structure. In contrast, the coordination polymer type {[Ln(NO(3))(3)(L(II))].nCH(3)OH}(n) displays a (3,3)-connected puckered two-dimensional net with 4.8(2) topological notation. The photophysical properties of the Sm, Eu, Tb and Dy complexes at room temperature are investigated. The present work substantiates the claim that the supramolecular structure as well as the luminescent properties of the coordination polymer can be tuned by varying either the backbone group or the terminal group of the organic ligand.     

Structure and dynamics of binary and ternary lanthanide(III) and actinide(III) tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione] (TTA) complexes. Part 2, the structure and dynamics of binary and ternary complexes in the Y(III)/Eu(III)-TTA-tributylphosphate (TBP) system in chloroform as studied by NMR spectroscopy

The stoichiometric reaction mechanisms, rate constants and activation parameters for inter- and intramolecular ligand exchange reactions in the binary Y/Eu(TTA)(3)(OH(2))(2)-HTTA and the ternary Y/Eu(TTA)(3)(OH(2))(2)-TBP systems have been studied in chloroform using (1)H and (31)P NMR methods. Most complexes contain coordinated water that is in very fast exchange with water in the chloroform solvent. The exchange reactions involving TTA/HTTA and TBP are also fast, but can be studied at lower temperature. The rate constant and activation parameters for the intramolecular exchange between two structure isomers in Y(TTA)(3)(OH(2))(2) and Y(TTA)(3)(TBP)(OH(2)) were determined from the line-broadening of the methine protons in coordinated TTA. The rate equations for the intermolecular exchange between coordinated TTA and free HTTA in both complexes are consistent with a two-step mechanism where the first step is a fast complex formation of HTTA, followed by a rate determining step involving proton transfer from coordinated HTTA to TTA. The rate constants for both the inter- and intramolecular exchange reactions are significantly smaller in the TBP system. The same is true for the activation parameters in the Y(TTA)(3)(OH(2))(2)-HTTA and the ternary Y/Eu(TTA)(3)(TBP)(OH(2))-HTTA systems, which are ΔH(≠) = 71.8 ± 2.8 kJ mol(-1), ΔS(≠) = 62.4 ± 10.3 J mol(-1) K(-1) and ΔH(≠) = 38.8 ± 0.6 kJ mol(-1), ΔS(≠) = -93.0 ± 3.3 J mol(-1) K(-1), respectively. The large difference in the activation parameters does not seem to be related to a difference in mechanism as judged by the rate equation; this point will be discussed in a following communication. The rate and mechanism for the exchange between free and coordinated TBP follows a two-step mechanism, involving the formation of Y(TTA)(3)(TBP)(2).     

Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence

Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2?:?3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.     

稀土螯合物发光体LB膜的研究(I)

稀土有机配合物的发光研究近年来取得了可喜的近展.铕(Ⅲ)、铽(Ⅲ)、钐(Ⅲ)与β-二酮(β-dik),三正辛基氧化膦(TOPO)所形成的螯合物,以及它们的硝酸盐与邻菲咯啉(Phen)所形成的螯合物都是高光效的发光体,有广阔的应用前景,在某些方面已获得应用.如能把这些具有发光功能的稀土螯合物组装成有序的分子组合体,则很可能在分子光学技术,光电子技术等领域发挥重要作用.如何组装?本文用LB 膜技术,通过交替成膜或混