2,5-二羟基苯甲醛缩肼席夫碱的性质和研究

设计和合成了一种双席夫碱。利用红外光谱对其结构进行表征,研究了其在不同溶剂中的紫外吸收光谱和荧光光谱,探究了过渡金属离子对紫外和荧光光谱的影响及聚集诱导发光(AIE)性质。结果表明,在不同溶剂中化合物的紫外光谱发生蓝移,荧光发射强度随溶剂极性增加强度减弱,且发生红移。通过紫外光谱和荧光光谱说明Fe~(3+)、Cu~(2+)在溶液中和化合物分子发生较强的相互作用,生成稳定配合物。同时该化合物没有表现出明显的AIE性质。     

一个芳环堆积共结晶化合物的合成与表征

在溶剂中,采用水热法合成得到了一个共结晶的芳环堆积化合物C_8H_5O_7S·C_(10)H_9N_2·(C_(10)H_8N_2)_(0.5)(C_(10)H_8N_2=2,2’-联吡啶)。采用X射线单晶衍射和元素分析对其结构和组成进行了表征。X射线单晶衍射表征结果表明,该化合物晶体属于三斜晶系。研究了该化合物的荧光光谱以及热稳定性,该化合物荧光发射峰在417nm,热稳定性较好。     

聚乙烯C–H伸缩振动二维红外光谱研究

在293~393 K范围内,分别测定聚乙烯(PE)的一维红外光谱、二阶导数红外光谱和去卷积红外光谱来确定PE分子结构。进一步采用二维红外光谱研究了聚乙烯亚甲基C–H伸缩振动模式(νCH2)的模式。研究发现,PE分子中存在晶区和非晶区。随着测定温度的升高,PE分子中νCH2红外吸收强度变化快慢顺序为:2 920 cm-1(νas(CH2)crystalline)2 930 cm-1(νas(CH2)amorphous)2 850 cm-1(νs(CH2)crystalline)2 858 cm-1(νs(CH2)amorphous)。此项研究显示出二维红外光谱在高分子材料热变性分析中的重大作用。     

新型染料BOPIM的制备及光谱性能测试

以2-醛基吡啶和邻苯二胺为起始原料,经两步反应合成了新型的BOPIM(Boron 2-(2-pyr-idyl)imidazole complex)荧光染料,并通过1 H NMR,13C NMR,高分辨质谱进行了结构鉴定。对该化合物的紫外-可见吸收及荧光光谱测试表明:该染料有较高的荧光量子产率,相对较大的Stokes位移;且荧光性能呈现明显的溶剂效应。     

聚酰胺-66的ν_(amide-Ⅲ)和ν_(amide-Ⅳ)三级红外光谱研究

在4 000~600 cm~(-1)的频率范围内,采用一维红外光谱,二阶导数红外光谱和四阶导数红外光谱研究了聚酰胺-66的分子结构。以聚酰胺-66的ν_(amide-Ⅲ)和ν_(amide-Ⅳ)为对象,采用变温红外光谱技术进一步开展了聚酰胺-66热稳定性的研究。实验发现,在303~393 K的温度范围内,聚酰胺-66的ν_(amide-Ⅲ)和ν_(amide-Ⅳ)对应的红外吸收频率均出现了明显的红移现象。首先分别开展了聚酰胺-66的ν_(amide-Ⅲ)和ν_(amide-Ⅳ)的二维红外光谱研究。实验发现:聚酰胺-66的ν_(amide-Ⅲ)的红外吸收频率包括:1 277 cm~(-1)(ν_(amide-Ⅲ-1))和1 269 cm~(-1)(ν_(amide-Ⅲ-2)),而随着测定温度的升高,聚酰胺-66的ν_(amide-Ⅲ)的红外吸收峰变化快慢顺序为1 269 cm~(-1)(ν_(amide-Ⅲ-2))1 277 cm~(-1)(ν_(amide-Ⅲ-1));聚酰胺-66的ν_(amide-Ⅳ)的红外吸收频率包括:939 cm~(-1)(ν_(amide-Ⅳ-1))和931 cm~(-1)(ν_(amide-Ⅳ-2)),而随着测定温度的升高,聚酰胺-66的ν_(amide-Ⅳ)红外吸收峰变化快慢顺序为931 cm~(-1)(ν_(amide-Ⅳ-2))939 cm~(-1)(ν_(amide-Ⅳ-1))。进一步同时开展了聚酰胺-66的ν_(amide-Ⅲ)和ν_(amide-Ⅳ)的二维红外光谱研究。随着测定温度的升高,聚酰胺-66的ν_(amide-Ⅲ)和ν_(amide-Ⅳ)的红外吸收峰变化快慢顺序为1 269 cm~(-1)(ν_(amide-Ⅲ-2))1 277 cm~(-1)(ν_(amide-Ⅲ-1))931 cm~(-1)(ν_(amide-Ⅳ-2))939 cm~(-1)(ν_(amide-Ⅳ-1))。本项研究拓展了三级红外光谱技术在高分子材料结构及热稳定性方面的研究范围。     

双对二甲氨基苯甲醛缩连氮的合成及其对金属离子的识别

以水合肼和对二甲氨基苯甲醛为原料设计合成了双对二甲氨基苯甲醛缩连氮(1),经元素分析、1H-NMR及质谱对其结构进行了表征。在甲醇-水(V/V=4:1)混合溶剂中采用UV-Vis光谱法和荧光光谱法研究了化合物1对H+、Li+、Na+、K+、Mg2+、Ca2+、Mn2+、Co2+、Ni2+、Zn2+、Cd2+、Hg2+及Cu2+的选择性识别性能。结果表明,化合物1的紫外-可见光谱仅对H+有特殊的选择敏感性;其荧光光谱对H+、Mn2+和Co2+有显著的识别传感能力,三种离子均可有效地猝灭化合物1的荧光。根据Stern-Volmer公式,Mn2+和Co2+对化合物1荧光的影响属于动态猝灭过程。     

高锰酸钾氧化法制备1,1′:3′,1″-三联苯-4,4″-二羧酸及其光学性质

以4,4″-二甲基-1,1′:3′,1″-三联苯(1)为原料,吡啶-水为混合溶剂,高锰酸钾为氧化剂,制备了1,1′:3′,1″-三联苯-4,4″-二羧酸(2),利用核磁共振氢谱、红外光谱、吸收光谱、荧光光谱等表征了化合物2的结构和性质,并考察了化合物1与高锰酸钾的物质的量比、反应时间和反应温度对收率的影响,进而确定了化合物2的优化合成条件,即以吡啶-水混合液(4∶11,V∶V)为反应溶剂,n(1)∶n(高锰酸钾)=1∶6.7,反应温度为95℃,反应时间为1.5h时,化合物2的产率为74.8%。     

1,8-萘酰亚胺类化合物的荧光光谱性能研究

研究了11种新型1，8-萘二甲酰亚胺类荧光化合物的荧光光谱性能。利用紫外光谱仪和荧光光谱仪测定了这两类化合物的紫外光谱和荧光光谱，分别得到最大吸收波长、最大激发波长、最大荧光发射波长，并以硫酸奎宁的0.5mol／l硫酸水溶液为参比标准，测定了各化合物的荧光量子产率在此基础上，研究了浓度、溶荆对荧光性能的影响、以及化合物结构与荧光性能的关系。结果表明，1，8-萘酰亚胺粪化合物随着浓度的增大，荧光光谱发生红移，且斯托克斯位移增大。随着溶剂极性的增大，最大荧光发射波长发生红移，斯托克斯位移增大，荧光量子产率增大在1，8-萘酰亚胺类化合物的4-位引入笨并呋喃取代基后，最大荧光发射波长红移70nm～100nm，斯托克斯位移增大20nm～50nm，荧光量子产率明显增大。     

分子内电荷转移化合物发光行为的研究——N,N-二甲氨基苯乙烯基偏二氰乙烯的发光行为

合成了二种新的分子内电荷转移化合物:双(p-N,N-二甲氨基苯乙烯基)偏二氰乙烯(Ⅱ)及(p-N,N-二甲氨基苯乙烯基)苯基偏二氰乙烯(Ⅱ)。并对它们在不同极性溶剂中的光谱和光物理行为进行了研究。结果表明:化合物(Ⅰ)的荧光量子产率随溶剂极性增大而不断提高,而化合物(Ⅱ)的荧光量子产率则随溶剂极性增大出现了一极大值。对这一现象的产生进行了初步讨论。     

双卟啉的超共轭效应对其光谱行为的影响

合成了2个双卟啉化合物(简称为(TPP)2p和(TPP)2n)和一个单卟啉化合物(简称TPPa),并进行了核磁共振表征。研究了卟啉环之间的超共轭效应对分子的单、双光子吸收行为的影响,经吸收光谱和荧光光谱证实,发现双卟啉(TPP)2p和(TPP)2n由于存在pπ共轭效应和σπ超共轭效应,使得双卟啉的吸收和荧光强度均比单卟啉TPPa要强得多。并计算三种卟啉在不同溶剂种光物理性质参数。     

由4-氨基二苯醚合成三苯二噁嗪荧光染料

以4-氨基二苯醚为原料合成了10个新结构三苯二口恶嗪型荧光染料,测定了它们在甲苯、氯仿、DMF、丙酮和乙醇中的吸收光谱和荧光光谱。结果表明,这些染料发色强度大(εm ax>7×104),荧光强度高(在甲苯中Ф=0.43~0.78),染料的摩尔消光系数、荧光量子产率和Stokes位移与溶剂极性参数ET之间呈线性变化关系。     

Synthesis, absorption and fluorescence properties of N-triazinyl derivatives of 2-aminoanthracene

N-(4,6-dichloro-1,3,5-triazin-2-yl)-2-aminoanthracene was synthesized by substitution of one chlorine atom of 2,4,6-trichloro-1,3,5-triazine with 2-aminoanthracene. A new series of N-triazinyl-2-aminoanthracenes was prepared by nucleophilic substitution of one or both chlorine atoms on N-(4,6-dichloro-1,3,5-triazin-2-yl)-2-aminoanthracene with electron-donating methoxy or phenylamino groups. The UV/Vis absorption, fluorescence and excitation spectra as well as the fluorescence quantum yields of the prepared compounds were measured in 1,4-dioxane, ethyl acetate, dibutyl ether and acetonitrile; nanosecond kinetics of the fluorescence decay was measured in different solvents. The influence of the character of the substituent on triazinyl ring and of the solvent polarity upon the absorption and fluorescence spectra and fluorescence quantum yields are discussed.     

三芳基-2-吡唑啉化合物分子内光诱导电荷转移过程的研究

本工作对带有不同取代基的1,3,5-三芳基-2-吡唑啉类化合物的稳态光物理行为进行了研究,从它们在不同极性溶剂中的吸收光谱和荧光发射光谱以及荧光量子效率的结果表明,这类化合物分子内共轭的及非共轭的光诱导电荷转移的趋向取决于上述两过程间的竞争。     

Absorption and fluorescence of soluble polar diketo-pyrrolo-pyrroles

Six soluble derivatives of 3,6-diphenyl-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione N-alkylated on pyrrolinone ring with polar substituents in para positions of pendant phenyl rings were synthesized; five of them are reported for the first time. Absorption and fluorescence spectra were studied in solvents of different polarity. The compounds show small solvatochromism of absorption and a moderate positive solvatochromism of fluorescence, especially when substituted by strong electron-donating piperidino substituent. A significant decrease of fluorescence quantum yields and its biexponential decay for dipolar derivatives in polar solvents was tentatively ascribed to the formation of twisted intramolecular charge transfer (TICT) excited state. All six compounds show fluorescence in polycrystalline solid-state with the maxima covering a range over 200 nm in visible and near infrared region.     

Absorption and fluorescence of soluble polar diketo-pyrrolo-pyrroles

Six soluble derivatives of 3,6-diphenyl-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione N-alkylated on pyrrolinone ring with polar substituents in para positions of pendant phenyl rings were synthesized; five of them are reported for the first time. Absorption and fluorescence spectra were studied in solvents of different polarity. The compounds show small solvatochromism of absorption and a moderate positive solvatochromism of fluorescence, especially when substituted by strong electron-donating piperidino substituent. A significant decrease of fluorescence quantum yields and its biexponential decay for dipolar derivatives in polar solvents was tentatively ascribed to the formation of twisted intramolecular charge transfer (TICT) excited state. All six compounds show fluorescence in polycrystalline solid-state with the maxima covering a range over 200 nm in visible and near infrared region.     

The synthesis,fluorescence behaviour and singlet oxygen studies of new water-soluble cationic gallium(III) phthalocyanines

The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.     

三苯二(口恶)嗪电子光谱的溶剂效应

本文测试了两个三苯二(口恶)嗪化合物在19种溶剂中的电子光谱。发现化合物的可见吸收光谱的两个吸收带的v_(max)分别与溶剂的存在着良好的线性关系。     

Solvatochromic Behaviour and Prototropic Studies of some oxazolones of electron donor-acceptor type

Solvatochromic and halochromic behaviour in the u.v.-vis absorption spectra of some substituted 4-arylidene-2-aryloxazol-5-ones ( 1–5 ) are studied. Positive and negative solvatochromism, depending on the substituent present, are observed in different hydrogen bonding donoracceptor (HBD-A) and hydrogen bonding acceptor (HBA) solvents. However, in non hydrogen bonding (NHB) solvents all compounds show a positive solvatochromism. A considerable intramolecular charge transfer interaction, between the donor and acceptor parts in the oxazolones studied, is observed. Small fluorescence quantum yields are observed for the oxazolones. In triethanolamine-acetone mixtures, the visible absorption spectra of the hydroxy substituted oxazolone shows an additional long-wavelength band suggesting the existance of prototropic equilibria. The prototropic equilibrium constants at different temperatures are determined.     

Photochemie substituierter Cycloheptatriene. XV. Zur Charakterisierung der Elektronischen Übergänge in 1-Aryl-4-(p-dimethylaminophenyl)-cycloheptatrienen

Photochemistry of Substituted Cycloheptatrienes. XV. About the Characterization of the Electronic Transitions in 1-Aryl-4-(p-dimethylaminophenyl)-cycloheptatrienes The absorption spectra of the title compounds are discussed in dependence on polarity of the solvent and its ability to form hydrogen bonds. The results suggest a hybridization of the N-atom of the dimethylamino group between sp³ and sp² in the ground state. Contrary to this, the nitrogen has sp²-hybridization in the short wavelength (SE) fluorescing state. In a second fluorescence state the geometry of the seven-membered ring should change. Therefore the viscosity of the solvents influences both the position and the quantum yield of this long wavelength emission (LE). The influence of polarity and viscosity of the solvents is described by multiple regression. The temperature dependence of fluorescence quantum yields is discussed, as well.     

不对称二苯乙烯基苯并(噁)唑类化合物的合成及光谱性能的研究

以对氰基氯苄为原料,与取代的邻氨基苯酚反应,合成了一系列标题化合物.测定了此类化合物的紫外光谱和荧光光谱,并以硫酸奎宁为参比标准测定了化合物的荧光量子产率.研究了分子结构与紫外光谱、荧光光谱的关系.