单氨基取代3∶1不对称酞菁锌的合成及其在有机溶剂中聚集状态的研究

Monoamino substituted asymmetrical phthalocyanine zinc(Ⅱ), 2-amino-9,10,16,17,23,24-hexapentyloxy phthalocyanine zinc(Ⅱ), was synthesized by statistical condensation and characterized by elemental analysis, UV-Vis, IR and TOF-MS. The aggregative behavior was studied in DMF, THF and CH₂Cl₂. The results show that it is not aggregateve in DMF and THF, whereas form dimer in CH₂Cl₂ at 8 × 10^-7～8 × 10^-6 mol·L^-1. The equilibrium constant for the dimer was calculated at the same time, indicating that the less polar solvent is unfavorable for the presence of the monomer.     

异硫氰酸铬(Ⅲ)二(18-冠-6)铵配合物的合成、特征和光化学

本文报道了标题中所指的配合物固体和单晶的制备,测定了IR,UV-Vis光谱以及该配合物在CH₃CN和DMF中的光化学性质。采用单晶X射线衍射测定了该配合物的结构,它属于单斜晶系,空间群P2₁/n,测定了固体配合物在CH₃CN和DMF中的量子产率Φ_NCS,并讨论了光反应机制。     

高选择性透过SO2气体分离膜研究 Ⅰ.丙基乙烯基亚砜改性聚乙烯醇功能高分子的合成

 本文研究聚乙烯醇与丙基乙烯基亚砜经Michael加成反应合成含亚砜基的改性聚乙烯醇功能高分子.用IR、¹H-NMR、X-射线衍射等鉴定反应产物.结果表明,随着亚砜基含量的增加聚合物的结晶性降低,而在冷水,DMSO,CH₃OH,C₂H₅OH和CH₂Cl₂中的溶解性提高.     

X@(HAlNH)12和X(HAlNH)12 (X＝F－, Cl－, Br－, O2－, S2－, Se2－)复合物的结构和稳定性

用DFT的B3LYP方法在6-31G(d)基组的水平上, 对闭式多面体簇合物(HAlNH)₁₂及其内含式X@(HAlNH)₁₂和外接式X(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, O^2－, S^2－, Se^2－)复合物的结构进行了构型优化和能量计算, 并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系, 最后得到复合物结构的稳定性信息, 具有T_h对称性的X@(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, S^2－, Se^2－)复合物和具有C₃对称性的O^2－@(HAlNH)₁₂复合物为内含式的基态结构, 从能量角度分析, 内含式复合物比外接式复合物的结构稳定.     

萘基桥联有机-无机杂化介孔材料的合成及其光学性质

以短链阳离子三聚表面活性剂C₁₀H₂₁N⁺(CH₃)₂(CH₂)₂N⁺(CH₃)(C₁₀H₂₁)(CH₂)₂N⁺(CH₃)₂C₁₀H₂₁]·3Br^?为结构导向剂, 通过2,7-二(3-三乙氧硅基氨丙酯基)萘(NIS)和四乙氧基硅烷(TEOS)共缩聚, 制备了有序的萘基桥联的杂化周期性介孔有机硅(PMOs). 样品通过X射线衍射(XRD)、高分辨透射电镜(HRTEM)、氮气吸附-脱附、差示扫描量热/热重分析(DSC/TGA)表征. 结果表明, 当NIS占NIS和TEOS总量40% (摩尔分数)时, 可以形成具有结晶态孔壁的有序介孔杂化材料. 当NIS含量低于或高于40%时, 分别形成无定形孔壁的有序介孔杂化材料和无孔杂化材料. 随着孔壁中萘基基团的增加, 由于有机基团之间π-π堆积作用增强, 杂化介孔材料显示良好的热稳定性. 由于在二氧化硅骨架中嵌入荧光萘基基团, 杂化有机-无机有序介孔材料显示了激基缔合物的光学行为. 随萘基基团含量的增加, 杂化材料的紫外吸收峰发生蓝移, 形成H聚集体; 由于聚集引起的荧光淬灭, 杂化材料的荧光量子产率明显降低.     

Li＋在基于N,N-二甲基甲酰胺混合溶剂中的溶剂化

利用红外和拉曼光谱技术研究了Li^＋在不同浓度、不同溶剂组成的LiBF₄/N,N-二甲基甲酰胺-乙腈、LiBF₄/N,N-二甲基甲酰胺-四氢呋喃电解质溶液中的优先溶剂化现象. 红外和拉曼光谱的分析表明, Li^＋主要与DMF分子相互作用, 导致该分子的C＝O伸缩振动谱带、N—C＝O形变谱带、CH₃摇摆谱带等发生了分裂. Li^＋与其它溶剂分子的相互作用较弱, 谱带的分裂现象并不明显. Li^＋溶剂化数的计算显示, Li^＋第一溶剂化层内DMF分子的数目一般大于2, 这说明 Li^＋在混合溶剂体系内优先与DMF分子相互作用. 量子化学计算支持了这一结论.     

三苯胺-噁二唑超支化共轭聚合物的多光子泵浦绿色荧光

采用钯催化Heck反应制备了一种新型三苯胺-噁二唑超支化荧光聚合物PI. 用飞秒Ti:sapphire激光研究了PI的三光子和双光子上转换荧光光谱, 激发波长位于近红外区(800~1350 nm). 在1280 nm和80 fs激光激发下, PI的三光子上转换荧光发射波长分别为525 nm(THF), 534 nm(CH2Cl2)和578 nm(DMF). 在800 nm和150 fs激光激发下, PI的双光子上转换荧光发射波长分别为527 nm(THF), 532 nm(CH2Cl2)和573 nm(DMF). 采用非线性透过率法测定荧光聚合物PI的三光子和双光子吸收系数. 系统研究了PI的线性吸收和透过、单光子荧光、荧光寿命、前线轨道能级及热稳定性. 实验结果表明, 三苯胺-噁二唑超支化共轭聚合物的多光子吸收和上转换荧光发射性能比树型分子或线型聚合物更为优异.     

X@(HAlNH)12和X(HAlNH)12 (X＝F－, Cl－, Br－, O2－, S2－, Se2－)复合物的结构和稳定性

用DFT的B3LYP方法在6-31G(d)基组的水平上, 对闭式多面体簇合物(HAlNH)₁₂及其内含式X@(HAlNH)₁₂和外接式X(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, O^2－, S^2－, Se^2－)复合物的结构进行了构型优化和能量计算, 并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系, 最后得到复合物结构的稳定性信息, 具有T_h对称性的X@(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, S^2－, Se^2－)复合物和具有C₃对称性的O^2－@(HAlNH)₁₂复合物为内含式的基态结构, 从能量角度分析, 内含式复合物比外接式复合物的结构稳定.     

两个蒽基Au(Ⅰ)配合物[Au(anbdtim)2]PF6和[Au(anbdtim)2][Au(CN)2]的结构调控和发光转换

合成了2个蒽基配合物[Au (anbdtim)₂]PF₆(1)和[Au (anbdtim)₂][Au (CN)₂](2),其中anbdtim=2-蒽基-4,5-双(2,5-二甲基(3-噻吩基))-1-甲基咪唑。它们含有不同的抗衡阴离子,1中的为PF₆^-,2中的为[Au (CN)₂]^-。这导致2个配合物在溶液和固态中都表现出显著不同的荧光。在CH₂Cl₂溶液中,配合物1和2的荧光发射波长分别为465和445 nm。在固态,1和2的荧光发射波长分别为450和478 nm。有趣的是,配合物2对苯分子很敏感,它在苯中的荧光发射波长为475 nm (量子产率Φ=66.5%),在CH₂Cl₂中为448 nm (Φ=22.9%)。此外,我们利用配合物2的苯溶液蒸发制备了蓝绿色发光固体2-benzene。当交替地除去和再次加入苯,固体2-benzene的荧光发射在蓝绿色(491 nm)和钢蓝色(460 nm)之间可逆地转换。在实验结果的基础上,我们讨论了抗衡阴离子和苯分子对1和2的发光行为的影响。     

两个4-连接配位网络的锌(Ⅱ)配位聚合物的合成、结构和荧光性质

以5-氨基四氮唑(HATz), 异烟酸(HPyc)和ZnSO₄·7H₂O或Zn(NO₃)₂·6H₂O为反应物, 在DMF溶剂热条件下分别得到了2个锌(Ⅱ)配位聚合物{[(CH₃)₂NH₂]·[Zn(ATz)(SO₄)]}_n (1)和{[Zn(ATz)(Pyc)]·0.5DMF}_n (2), 并对它们的组成和结构进行了表征。配合物1是由4-连接(4, 4)网络拓扑的[Zn(ATz)(SO₄)]_n^n-二维阴离子层和[(CH₃)₂NH₂]⁺阳离子间通过氢键作用形成的二维波浪层结构。配合物2则是1个二重穿插的4-连接金刚烷拓扑的三维微孔金属-有机框架结构, 客体DMF分子填充在孔道内。室温下的固体荧光实验表明, 在350 nm的光激发下, 配合物1和2分别在为445 nm和458 nm处出现强烈的荧光发射。     

Single light emitters in electrospun polymer nanofibers: Effect of local confinement on radiative decay

The fabrication of light emitting polymer nanofibers by electrospinning of polymer solutions containing either fluorescent organic dye molecules or luminescent semiconductor nanoparticles (quantum dots) is presented. The fluorescence spectra and lifetime of the embedded emitters, down to the level of single molecules were investigated. While the average fluorescence lifetime of single molecules embedded in poly(methyl methacrylate) fibers appears independent of the fiber diameter, the single molecule approach reveals a significant broadening of the fluorescence lifetime distribution for fibers with diameters below the wavelength of light.     

Component analysis of the fluorescence spectra of a lignin model compound

In order to test whether lignin fluorescence originates from discrete fluorophores, fluorescence emission spectra of the lignin model dehydrogenative polymer (DHP) were analyzed by the band deconvolution method and time-resolved analysis of both the excitation and emission spectra. Two series of 22 fluorescence emission spectra of DHP in chloroform/methanol (3:1, v/v) solution, and as a solid suspension in water, were deconvoluted into three fluorescence and one Raman Gaussian components. Emission spectra were obtained by stepwise variation of the excitation wavelength from 360 to 465 nm. Deconvolution was performed by nonlinear fitting of all three Gaussian parameters: area, width and position. Position of all components in a series was treated as a random variable and its approximate probability distribution (APD) calculated from a series of histograms with increasing number of abscissa intervals. A five peak multimodal APD profile was obtained for both series of DHP emission spectra. The mean fluorescence lifetime varied with wavelength both in the emission and the excitation decay-associated spectra (DAS), where four kinetic components were resolved. The shapes of the excitation spectra of the four components were quite different and gradually shifted bathochromically. The multicomponent nature of the DHP emission spectra along with the changes in the mean fluorescence lifetime and the form of the excitation DAS of the four components give evidence of the heterogeneous origin of fluorescent species emitting in the visible.     

Synthesis and fluorescence characterization of MEHPPV oligomers

Trimer, tetramer, and pentamer oligomers based on the polymer backbone structure of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV) have been synthesized by Horner-Wadsworth-Emmons reactions. The fluorescence spectra, emission quantum yields, and lifetimes of the oligomers have been characterized in dilute chloroform solutions. The oligomers exhibit a sequential increase in absorption and emission wavelength maxima and a decrease in fluorescence lifetime as the π conjugation length is increased. The shortening in excited state lifetime is shown to be due to an increase in the rates of both radiative and nonradiative processes. The absence of a mirror-image relationship for the absorption and fluorescence spectra of the oligomers is attributed to the photoexcitation of a range of torsional configurations followed by relaxation to a more planar arrangement that then emits.     

Characteristics of Twisted Intramolecular Charge‐Transfer State in a Hyperbranched Conjugated Polymer

A hyperbranched conjugated polymer functionalized in periphery with N,N‐dimethylaniline was synthesized and characterized. Solvatochromic shifts in both absorption and fluorescence spectra, the effects of solvent polarities on the fluorescence quantum yield and fluorescence lifetime were investigated to probe the formation of an intramolecular charge transfer (ICT) state. The peak position of the emission band arising from the ICT state is red‐shifted, and the fluorescence quantum efficiency of the polymer decreases with increasing polarity of the solvents.     

Synthesis and characterization of a Eu-containing polymer precursor featuring thenoyltrifluoroacetone and 5-acrylamido-1,10-phenanthroline

A polymerizable ligand, 5-acrylamido-1,10-phenanthroline (L), was synthesized. Its Eu(III) complex with 2-thenoyltrifluoroacetone (HTTA) was prepared and characterized by elemental analysis, IR, MS, and ¹H NMR spectra. The photophysical properties of the complex were studied in detail by using UV, luminescence spectra, luminescence lifetime and quantum yield. The complex shows a remarkable luminescence quantum yield at room temperature (40.1%) upon ligand excitation and a long ⁵D₀ lifetime (590 μs), which makes it not only a promising light-conversion molecular device but also an excellent luminescent polymer precursor.     

两种螺旋藻核复合物结构特性的研究

从螺旋藻藻胆体中分离出两种复合物:核复合物(APC)和杆-核复合物(APCR),通过吸收光谱及其二阶导数光谱、荧光光谱研究了二者的结构和光谱特性,讨论了在这两种沉降系数分别为36S和16S的超分子复合物内几种连接多肽:L^29.5,L_C^8.9和LCM对复合物结构和功能的影响。     

8-羟基喹啉衍生物及其金属配合物的合成与光致发光特性

设计合成了三种新型的8-羟基喹啉衍生物配体: 5-[(4-E-苯乙烯基)-苯甲亚胺基]-8-羟基喹啉(1), 5-[(4-溴-2-氟)-苯甲亚胺基]-8-羟基喹啉(2)和N-乙基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑(3), 以及它们相应的金属配合物, 产物经质谱(MS)、元素分析(EA)、红外光谱(IR)、紫外光谱(UV)、核磁共振氢谱(¹H NMR)进行表征, 并测定了它们的荧光性质. 结果与8-羟基喹啉比较表明, 5位和2位取代8-羟基喹啉衍生物的荧光发生了明显的红移. 同时测定了配合物(3)₂Zn的荧光寿命, 结果表明, N-乙基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑锌配合物表现出较长的荧光寿命.     

Synthesis of a Novel m-Substituted Poly(phenoxy-imine) and Investigation of its Fluorescence and Some Properties

Oxidative polycondensation of 3-((2-phenylhydrazono)methyl)phenol (3-PHMP), a new m-substituted poly(phenoxy-imine), was studied using oxidants such as sodium hypochlorite, air (O₂) and hydrogen peroxide in an aqueous alkaline medium under various polymerization conditions. The macromolecular structure and optical properties of the polymer were characterized with elemental analysis, Size Exclusion Chromatography (SEC), Fourier Transform Infrared (FTIR), Nuclear Magnetic Resonance (NMR), absorption and fluorescence spectroscopy techniques. As a result of fluorescence measurement, the fluorescence lifetime of poly(3-PHMP) in DMF was calculated as 2.88 ns (χ²= 1.12). An electrochemical property the monomer and polymer were also studied using Cyclic Voltammetry (CV) technology. According to the CV measurements, the electrochemical band gaps (E_g′) of 3-PHMP and poly(3-PHMP) were found to be 2.64 and 1.94 eV, respectively. Electrical conductivity of the polymer was measured by the four-point probe technique. The electrical conductivity of poly(3-PHMP) was found to be ～3.2 × 10^?2S/cm. Thermo Gravimetric Analysis (TGA) revealed poly(3-PHMP) to be stable against thermo-oxidative decomposition. In addition, the in vitro antimicrobial activities of the synthesized compounds were tested on various microorganisms.     

Preparation and luminescence properties of tris(bipyridine) ruthenium(II)-containing vinyl polymers: Ru(bpy)2 (poly-6-vinyl-2,2′-bipyridine)Cl2 and Ru(bpy)2(poly-4-methyl-4′-vinyl-,2,2′-bipyridine)Cl2

Ruthenium (II) complex-containing polymers were prepared and characterized by absorption and luminescence spectra, luminescence quantum yield, and luminescence lifetime. The polymers are Ru(bpy)₂(poly-6-vinyl-2,′2-bipyridine)CI₂ ( 1 ) and Ru(bpy)₂(poly-4-methyl-4′-methyl-4′ -vinyl-2,2′-bipyridine)CI₂ ( 2 ). The absorption spectra and luminescence spectra of polymers 1 and 2 were substantially the same as that of Ru(bpy)₃CI₂. The lifetime of polymers 1 and 2 was similar to that of the respective monomer model compounds. The lifetime of polymer 1 was very short (ca. 13 ns) in comparison to Ru(bpy)₃CI₂ (660 ns), whereas the lifetime of polymer 2 (660 ns) was similar to that of Ru(bpy)₃CI₂. The temperature-dependency of the lifetime was discussed in terms of Watts' model.     

Tropone‐containing π‐conjugated polymers: Annulation of tropone onto benzene ring in the conjugated polymer

Tropone‐fused, various π‐conjugated polymers ( P2 – P5 ) were synthesized by the palladium‐catalyzed coupling reaction of 1,4‐dibromo‐6,8‐dimethyl‐7H‐benzocyclohepten‐7‐one with aromatic divinyl, diboronic acid, and diethynyl compounds. The molecular orbital calculation of the model compounds was performed to discuss effective conjugation length of the repeating unit of the polymers. The absorption spectra of phenylenevinylene‐type polymers shifted to longer wavelengths than the model compounds by about 60 nm. They exhibited green fluorescence [λ_max(em) = 544 and 561 nm]. The absorption spectrum of a phenylene‐type polymer blueshifted by 10 nm; however, that of a phenyleneethynylene‐type polymer redshifted by 83 nm as compared with their model compounds. They showed fluorescence with peak maxima at 457 and 489 nm, respectively. As a result, the absorption spectra of phenylene‐ and phenylenevinylene‐type polymers blueshifted, but that of a phenyleneethynylene‐type polymer redshifted by the annulation of tropone onto a benzene ring in the conjugated polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1208–1215, 2004