2-巯基-4,6-二甲基嘧啶锌(Ⅱ)配合物研究

本文合成了2-巯基-4,6-二甲基嘧啶配体(HL)及其锌(Ⅱ)配合物.通过元素分析、质谱分析(ESI-MS)、红外光谱、紫外光谱和DSC热分析对配体和配合物进行了表征,推测出配体和配合物可能的组成和结构.对绿豆、小麦、玉米的培养实验表明,10-4g/g浓度的锌(Ⅱ)配合物溶液对种子的生长有一定调节作用.     

单-马来二腈基二硫烯-β-环糊精异构体在溶液中的不同组装行为

通过单-2-对甲苯磺酰基-β-环糊精(1)与马来二腈基二硫烯钠盐的取代反应制得单-2-马来二腈基二硫烯-β-环糊精(2),并经红外光谱、紫外光谱、热重分析、1H和13C NMR等手段对产物进行了表征.虽然化合物2的异构体--单-6-马来二腈基二硫烯9-β-环糊精在溶液中因为相互包合作用而在圆二色性光谱中产生分裂的Cot...     

1,1-二(2,4,6-三硝基苯甲酰胺基)-2,2-硝基乙烯的合成

以1,1-二氨基-2,2-二硝基乙烯(FOX-7)和2,4,6-三硝基苯甲酰氯(TNBC)为原料反应合成得到了1,1-二(2,4,6-三硝基苯甲酰胺基)-2,2-二硝基乙烯,并通过单因素试验和正交试验方法,分别探讨了反应介质、缚酸剂、反应温度和反应时间等对产物产率的影响,得到适宜的工艺条件为:FOX-7与TNBC物质的量的比1∶2.4,以四氢呋喃(THF)为反应介质,N,N-二甲基甲酰胺(DMF)为缚酸剂,反应温度0℃,反应时间48 h,产率可达94％.采用紫外可见光谱(UV-Vis)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)、红外光谱(FT-IR)、质谱(MS)及元素分析等对产物的结构进行了表征.利用差热分析仪对产物热稳定性进行了研究,结果表明,产物在空气中分解峰值温度为167℃,理论计算爆速为7.434km· s-1,爆压为23.67 GPa.     

二-(2-羟基-5-长链烷基苯基)-甲烷的合成

以脂肪酸、苯酚为原料, 经酰化反应、酯化反应、Fries重排、黄鸣龙还原等步骤, 得到正构长链烷基酚, 再与多聚甲醛在酸性催化剂下进行缩合反应, 生成二-(2-羟基-5-长链烷基苯基)-甲烷, 用核磁共振氢谱和碳谱、红外光谱和元素分析对产物进行了结构鉴定. 据上述反应路线, 以工业品壬基酚和多聚甲醛为原料, 合成出了二-(2-羟基-5-壬基苯基)-甲烷, 并对其工艺条件进行了研究. 结果表明, 选用草酸作催化剂, 烷基酚和甲醛物质的量比为2∶1, 130 ℃反应4 h, 产物产率达到60%, 且反应转化率和选择性分别为63%和95%.     

3,4-二羟基苯甲酸镉配合物的合成,结构表征及荧光性质

采用碳酸镉和3,4-二羟基苯甲酸、2,2’-联吡啶合反应得到了配位聚合物[Cd(C7H5O4)2·(H2O)3·2H2O(1).采用元素分析、红外光谱、荧光光谱对配合物进行了表征.用X射线单晶衍射仪测定了配合物的晶体结构.配合物为单斜晶系,P2(1)/c空间群,昌胞参数Z=4,a=0.78338(8)nm,b=1.98...     

2,6-二氨基-3,5-二硝基吡啶-1-氧化物的合成新方法

研究了2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)的合成新方法. 以2,6-二氨基吡啶为起始原料, 经酰基化、N-氧化、硝化三步反应得到ANPyO, 总收率为75%. 测试了ANPyO的爆速、爆压、DSC, 以及电火花感度和落锤感度, 同1,3,5-三氨基-2,4,6-三硝基苯(TATB)的性能进行了对比, 结果表明ANPyO综合性能和TATB基本相当. 用1H NMR, MS和红外光谱对ANPyO及其中间体结构进行了表征.     

9,10-二氢化菲在三氟化硼乙醚-浓硫酸混酸中的电化学聚合

在三氟化硼乙醚(BFEE)-浓硫酸混合电解质体系中直接氧化9,10-二氢化菲获得了高质量聚(9,10-二氢化菲)膜, 其电导率为3.8×10－1 S/cm. 9,10-二氢化菲在BFEE＋10%浓硫酸体系中的起始氧化电位为0.93 V vs. SCE, 远低于其在乙腈＋0.1 mol/L Bu4NBF4溶液中的起始氧化电位(1.75 V vs. SCE). 在BFEE＋10%浓硫酸体系中获得的聚(9,10-二氢化菲)膜具有良好的电化学性质. 聚合物部分溶于二甲基亚砜、四氢呋喃、氯仿等极性溶剂. FT-IR和量化计算表明聚合反应主要发生在2, 7位或者3, 6位. 荧光光谱和热重分析表明聚合物是一种良好的蓝色荧光材料且具有良好的热稳定性.     

新的稀土Eu,Tb(Ⅲ)β-二酮三元配合物的合成与光谱性质

采用Claisen缩合反应合成了一种β-二酮1-(4-氨基苯)-3-苯基丙烷-1,3-二酮(L:C15H13NO2),以元素分析和1H NMR谱确定了其组成,核磁和红外分析结果表明L主要以烯醇式存在。以L为第一配体,分别以邻菲罗啉(phen),2,2’-联吡啶(bipy)为第二配体,合成了新的稀土Eu,Tb(Ⅲ)三元配合物。通过元素分析、红外光谱、紫外光谱、磷光光谱和荧光光谱对合成的配合物进行了表征。荧光光谱表明:稀土铽配合物的发光性能优于稀土铕配合物,进一步研究表明配体L与Tb3+间能级差较匹配,分子内传能效率高;phen对配合物的荧光敏化效果优于bipy,表明第二配体的刚性和共轭性越大,配合物的发光性能越好。     

1,5-二芳基-3-(2-羟基-4,6-二甲氧基苯基)-2-吡唑啉的合成及氟离子荧光探针行为

设计合成了8个1,5-二芳基-3-(2-羟基-4,6-二甲氧基苯基)-2-吡唑啉化合物4a~4h. 它们的结构经由IR、1H NMR、MS和元素分析确认. 测定了它们的紫外光谱和荧光光谱, 研究了它们对氟离子的选择性识别作用, 发现化合物4a,4c和4d均可选择性地识别氟离子, 其中4a和4c作为识别氟离子的荧光探针, 受常见离子干扰较小, 选择性较高.     

含二乙炔类共轭聚合物的合成及性能研究

在以CuCl和四甲基乙二胺(TMEDA)作为催化剂和邻二氯苯作溶剂条件下,以二-(4-乙炔苯基)-4-辛氧基苯胺(M1)和3, 6-双(乙炔基)-N-辛基咔唑(M2)作为单体,通过Glaser-Hay氧化偶联反应合成了含有咔唑和三苯胺结构单元的聚芳烃二乙炔共轭聚合物.采用红外光谱、核磁共振谱、热失重分析、紫外吸收光谱和荧光光谱等方法对聚合物进行结构表征与性能测试.所得到的聚合物都溶于普通的有机溶剂(如四氢呋喃、二氯甲烷、氯仿、甲苯等).结果表明,聚合物具有优异的热稳定性,热失重5 %时,分解温度在400℃以上;在光激发的条件下,聚合物在二氯甲烷溶液中发射蓝光.     

Synthesis of Poly[（3-octanoylpyrrole-2,5-diyl）-p-（N, N-dimethylamino）benzylidene] and Its Properties by Nitrogen Ion Implantation

Introduction Nonlinearoptical(NLO)organicpolymers havereceivedincreasingattentionbecauseoftheir excellentbehaviorandthegoodprospectsoftheir applicationsinhigh-techareas,suchasoptical communication,high-densityopticalstorageand all-opticalinformationprocess.Poly(pyrrolylme- thine)isanNLOmaterialwithpromisingapplica- tions[1_3].However,itssolubilityandfilm-forming performancearepoor.Inthispaper,anovelsolu- blepoly(pyrrolylmethine),poly[(3-octanoyl-pyr- role-2,5-diyl)-p-(N,N-dimethylamino)ben…     

Cationic polythiophene-surfactant self-assembly complexes: phase transitions, optical response, and sensing

The absorption and photoluminescence spectra of the cationic conjugated polyelectrolyte poly[3-(6-trimethylammoniumhexyl)thiophene] (P3TMAHT) were observed to be dramatically altered in the presence of anionic surfactants due to self-assembly through ionic complex formation. Small-angle neutron scattering (SANS), UV/vis, and photoluminescence spectroscopy were used to probe the relationship between the supramolecular complex organization and the photophysical response of P3TMAHT in the presence of industrially important anionic surfactants. Subtle differences in the surfactant mole fraction and chemical structure (e.g., chain length, headgroup charge density, perfluorination) result in marked variations in the range and type of complexes formed, which can be directly correlated to a unique colorimetric and fluorimetric fingerprint. Our results show that P3TMAHT has potential as an optical sensor for anionic surfactants capable of selectively identifying distinct structural subgroups through dual mode detection.     

有机改性先驱体对含铕配合物的凝胶玻璃结构及性能的影响

分别采用γ-缩水甘油氧基三甲氧基硅烷(CH₂OCHCH₂O(CH₂)₃Si(OCH₃)₃) (GPTMS), 甲基三甲氧基硅烷(MTMS)和乙烯基三乙氧基硅烷(VTES)作为有机改性先驱体, 采用原位合成技术, 用溶胶-凝胶法制备了Eu^3＋, β-二酮噻吩甲酰三氟丙酮(TTA)及协同体1,10-菲啰啉(phen)共掺的三种有机改性二氧化硅(ormosil)玻璃. 测量了它们的发射光谱和红外光谱, 并进行了XRD, SEM和TG-DSC测试. 探讨了不同有机改性先驱体及热处理温度对原位合成的稀土有机配合物掺杂二氧化硅凝胶玻璃的发光性能、热稳定性及机械性能的影响. 结果表明, 有机改性先驱体能使凝胶玻璃结构致密, 但同时热稳定性降低; 对于荧光性能, MTMS和VTES可使其有一定的提高, 但它们的最大含量不能超过50%, 否则凝胶易失透, 而GPTMS能大幅提高凝胶的荧光性能. 通过综合比较, 选取出各种性能都较好的配方, 为今后制备较实用的具有较强荧光的含铕的凝胶玻璃提供了一定的依据.     

Synthesis and Characterization of Highly Efficient Photoluminescence Gd doping Hexagonal CePO_4 (One-dimensional Nanowires)

Rare earth phosphates have been used extensively in luminescent phosphors. Hexagonal Ce_(1-x)Gd_xPO_4 with crystal field manipulation was successfully synthesized using a hydrothermal method. The photoluminescence emission intensity of hexagonal CePO_4 was obviously enhanced by the crystal structure manipulation with gadolinium ions codoping. Compared to pure CePO_4, the intensity photoluminescence was enhanced about 15 folds with x = 0.05. The effect of gadolinium doping was systematically investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and photoluminescence spectroscopy. Crystal field asymmetry can be effectively tuned by different amount of Gd~(3+) codoping, and the crystal field asymmetry is conductive to electron population of high energy level of Ce~(3+) ions. This material has potential applications in optics, electronics fields, and so on. Meanwhile, the method can be extended to another kind of high performance photoluminescence materials preparation.     

Synthesis, surface morphology, and photoluminescence properties of anatase iron-doped titanium dioxide nano-crystalline films

Iron (Fe)-doped (0 to 4%) TiO(2) nano-crystalline (nc) films with the grain size of about 25 nm have been deposited on n-type Si (100) substrates by a facile nonhydrolytic sol-gel processing. X-ray diffraction measurements prove that the films are polycrystalline and present the pure anatase phase. X-ray photoelectron spectroscopy spectra indicate that the chemical valent state of Fe element is +3 and the Fe(3+) ions replace the Ti(4+) sites. The Fe dopant effects on the surface morphology, microstructure, and dielectric functions of the nc-Fe/TiO(2) films have been studied by atomic force microscope, ultraviolet Raman scattering and spectroscopic ellipsometry. With increasing Fe composition, the intensity of Raman-active mode B(1g) increases, while that of the A(1g) phonon mode decreases. The dielectric functions have been uniquely extracted by fitting ellipsometric spectra with the Adachi's dielectric function model and a four-phase layered model. It is found that the real part of dielectric functions in the transparent region and the optical band gap slightly decrease with the Fe composition due to the introduction of acceptor level Fe t(2g). Finally, the composition and temperature dependence of the surface and lattice defects in the Fe/TiO(2) films have been investigated by photoluminescence spectra in detail. At room temperature, the emission intensities decrease with increasing Fe compositions since the Fe incorporation could prolong the radiative lifetime and/or shorten the non-radiative lifetime. By analyzing the low temperature photoluminescence spectra, the intensities and positions of five emission peaks and shoulder structure can be unambiguously assigned. The phenomena could be reasonably explained by the physical mechanisms such as oxygen vacancies, localized excitons, self-trapped excitons, and indirect transitions, which are strongly related to the electronic band structure perturbed by the Fe doping.     

Photoluminescence response of terbium-exchanged MFI-type materials to Si/Al ratio, texture, and hydration state

Terbium-exchanged MFI zeolite type materials, i.e., microporous-mesoporous Zeotile-1 with the Si/Al ratio in the range 33-200, Zeogrid with the Si/Al ratio of 75, and nanocrystalline MFI with the Si/Al ratio of 75, were prepared via an ion exchange procedure. All of these zeolites were investigated by means of time-resolved photoluminescence techniques in various hydration states: as-synthesized (hydrated), calcined (heated at 450 degrees C in air), and rehydrated (after a six-month exposure to the atmospheric moisture). The photoluminescence decays and spectra were analyzed by discrete exponential fitting, distribution lifetimes analysis, and area-normalized time-resolved photoluminescence spectra. The results sustained a single average terbium species coordinated to both water molecules and framework oxygens in the hydrated zeolites. The framework contribution increased with the Si/Al ratio in Zeotile-1 and was greatest for the nanocrystalline MFI zeolite. For the calcined Zeotile-1 and Zeogrid, two main terbium species of different environments were found. For the nanocrystalline Tb3+-MFI, a distinct number of species could not be inferred, indicating a more heterogeneous distribution. Rehydration further differentiated among the Tb3+-exchanged zeolites. Photoluminescence line shape and decay of Tb3+-Zeotile-1 were between those of the hydrated and calcined states indicating a slow rehydration rate in contrast with the photoluminescence properties of Tb3+-MFI, which fully recovered the values of the hydrated state. Tb3+-Zeogrid presented an intermediate case: while the PL line shape was fully restored to that measured for the hydrated sample, the decay was still longer than that measured with the hydrated sample. Terbium photoluminescence response related to zeolite texture, Si/Al ratio, and hydration state suggest different sitting and location of terbium in Zeotile-1, Zeogrid, and nanocrystalline MFI materials. In mesoporous Zeotile-1 and Zeogrid, the results sustained two types of terbium sites: one on the internal surface of mesopores, the other inside the pores, while for the nanocrystalline MFI, terbium sites inside the pores predominate.     

Solid-state supramolecular organization, established directly from powder diffraction data, and photoluminescence efficiency of rigid-core oligothiophene-S,S-dioxides

The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene-4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO.     

Er2O3的光致发光光谱,吸收光谱和Raman光谱

在可见激光的激发下,Ｅｒ２Ｏ３粉晶样品的Ｒａｍａｎ光谱易受Ｅｒ＾３＋光致发光光谱的干扰。本文利用同一Ｒａｍａｎ光谱仪测得Ｅｒ２Ｏ３的高分辨可见光吸收光谱和激发光谱。     

An amphiphilic approach to nanocrystal quantum dot-titania nanocomposites

The addition of octylamine-modified poly(acrylic acid) to nanocrystal quantum dots (NQDs) results in robust, alcohol-soluble nanoparticles that can be readily incorporated into titania matrices without large changes in photoluminescence quantum yields. This approach relies on the amphiphilic nature of the polymer to create an NQD-polymer complex in which the alkyl chains interact with the hydrophobic part of the NQD, leaving the polar carboxylic acid groups on the periphery. This procedure is applicable to hydrophobically capped NQDs of a variety of shapes and compositions, making it a truly generalized route to nanocrystal-titania nanocomposites.     

KMnF3晶体的简单溶液合成及发光特性研究

Pure complex fluorides of KMnF3 crystal of spherical plate with a diameter of about 300 nm were successfully prepared by a simple aqueous synthesis method at room temperature. The sample was characterized by X-ray diffractometer (XRD), transmission electron microscopy, and selected area electron diffraction. An XRD result proves that the product is KMnF3 of perovskite-structure. By TEM and SAED results, it is found that the spherical plate morphology of sample is formed by self organization of KMnF3 grains. The sample shows two strong emissions at 416 and 438 nm, some discussion is made about the photoluminescence spectra and the resource of the emissions, at the same time, with the formula: Eem=-16963+164R and the photoluminescence spectrum, the bond distance of Mn-F could be estimated. Based on the obtained data it is easy to know the crystal parameter of samples with the perovskite-structure by results of photoluminescence spectra.