含咔唑基团芘类荧光材料的合成与发光性质

以1-溴芘、1,6-二溴芘和9-对乙炔苯基咔唑为原料,通过Sonogashira偶联反应合成了1-[4-(9-咔唑)苯乙炔基]芘和1,6-二[4-(9-咔唑)苯乙炔基]芘两种荧光分子。经熔点、核磁共振氢谱以及元素分析等结构表征,对中间体和目标产物的紫外-可见吸收、荧光发射以及结构与性质之间的构效关系进行了研究。通过结构修饰,可有效调节此类分子的吸收及发射性质。当芘单元作为中心电子受体,以4-苯乙炔基为桥连基,引入咔唑基团作为电子给体时,其分子共轭程度、结构刚性和分子内电荷转移能力显著提高。相对于D-π-A结构的单取代化合物,双取代D-π-A-π-D结构分子的最大发射峰由422 nm红移至446 nm,荧光量子效率由0.64提升至1.08。该类化合物可作为高效的蓝光荧光材料,应用于有机光致/电致发光材料以及有机发光二极管等领域。     

含咔唑基团芘类荧光材料的合成与发光性质

以1-溴芘、1,6-二溴芘和9-对乙炔苯基咔唑为原料,通过Sonogashira偶联反应合成了1-（4-（9-咔唑）苯乙炔基）芘和1,6-二（4-（9-咔唑）苯乙炔基）芘两种荧光分子。经熔点、核磁共振氢谱以及元素分析等结构表征,对中间体和目标产物的紫外-可见吸收、荧光发射以及结构与性质之间的构效关系进行了研究。通过结构修饰,可有效调节此类分子的吸收及发射性质。当芘单元作为中心电子受体,以4-苯乙炔基为桥连基,引入咔唑基团作为电子给体时,其分子共轭程度、结构刚性和分子内电荷转移能力显著提高。相对于D-π-A结构的单取代化合物,双取代D-π-A-π-D结构分子的最大发射峰由422 nm红移至446 nm,荧光量子效率由0.64提升至1.08。该类化合物可作为高效的蓝光荧光材料,应用于有机光致/电致发光材料以及有机发光二极管等领域。     

一种共轭炔基咔唑染料分子的合成及光谱性质研究

以二苯硫醚和咔唑为原料,合成了一种以碳碳三键作为桥接基团的新共轭炔基咔唑分子4,4'-二((N-乙基咔唑-3)-乙炔基)苯基硫醚(CZ-S-CZ),其结构经IR、~1HNMR和~(13)CNMR进行表征。通过紫外-可见吸收光谱研究表明,该物质在300~400 nm有较强的吸收。单光子荧光发射光谱研究表明,该化合物的单光子荧光最大发射波长是382 nm,荧光量子产率达到0.4。双光子激发荧光光谱研究表明,CZ-S-CZ在750~780 nm间具有双光子吸收性能,其双光子吸收截面最大可以达267.2 GM。     

2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯(DCHO)的合成。用核磁、红外和元素分析进行了表征。测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面。在800 nm的飞秒脉冲激光激发下,标题化合物发出很强的绿色上转换荧光。化合物2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的最大吸收波长、单光子发射波长、最大双光子荧光波长、荧光量子产率、双光子吸收系数及双光子吸收截面分别是393 nm、470 nm、475 nm、0.12、0.8 cm/GW、270 GM。这些数据表明,对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,DCHO是双光子荧光显微与成像应用的一个良好的候选材料。     

2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯(DCHO)的合成.用核磁、红外和元素分析进行了表征.测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面.在800 nm的飞秒脉冲激光激发下,标题化合物发出很强的绿色上转换荧光.化合物2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的最大吸收波长、单光子发射波长、最大双光子荧光波长、荧光量子产率、双光子吸收系数及双光子吸收截面分别是393 nm、470 nm、475 nm、0.12、0.8 cm/GW、270 GM.这些数据表明,对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,DCHO是双光子荧光显微与成像应用的一个良好的候选材料.     

2,5-二氰基-1,4-二（3′,4′,5′-三甲氧基苯乙烯基）苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(3′,4′,5′-三甲氧基苯乙烯基)苯(TMOS)的合成和非线性光学性质。用核磁、红外和元素分析进行了表征。测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面。在800 nm的飞秒脉冲激光激发下,目标化合物发出很强的黄绿色上转换荧光。TMOS的最大吸收波长、单光子荧光波长、双光子荧光波长、荧光量子产率、双光子吸收系数、最大双光子吸收截面及双光子荧光寿命分别是395 nm、523 nm5、26 nm、0.26、1.2 cm.GW-14、05 GM、230 ps。这些数据表明对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,TMOS是细胞中DNA双光子荧光显微与成像应用的良好候选材料。     

2,5-二氰基-1,4-二(3'',4'',5''-三甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(3′,4′,5′-三甲氧基苯乙烯基)苯(TMOS)的合成和非线性光学性质.用核磁、红外和元素分析进行了表征.测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面.在800 nm的飞秒脉冲激光激发下,目标化合物发出很强的黄绿色上转换荧光.TMOS的最大吸收波长、单光子荧光波长、双光子荧光波长、荧光量子产率、双光子吸收系数、最大双光子吸收截面及双光子荧光寿命分别是395 nm、523 nm、526 nm、0.26、1.2 cm·GW-1、405 GM、230 ps.这些数据表明对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,TMOS是细胞中DNA双光子荧光显微与成像应用的良好候选材料.     

两个D-π-A型双氰基二苯乙烯双光子荧光染料的合成

该文合成了两个以双氰基二苯乙烯为母体的D-π-A型双光子荧光染料,并以其作为模型化合物对双氰基与末端取代基对双光子吸收的影响进行了系统研究。两个化合物(DMO和DMA)具有大的双光子吸收截面(δ)。含有末端氨基的DMA较末端甲氧基的DMO具有更长的发射波长〔λem(DMA)=554 nm>λem(DMO)=459 nm〕、更大的双光子吸收截面〔δ(DMA)=3 650 GM>δ(DMO)=830 GM〕和更高的荧光量子产率〔η(DMA)=0.456>η(DMO)=0.294〕。理想的末端取代基不是烷氧基而是取代氨基。这类双氰基二苯乙烯染料拥有小的分子尺寸、大的δ(830～3 650 GM)、长的发射波长(459～554 nm)和大的斯托克斯位移(St)(131～150 nm),是比较理想的用于双光子荧光标记和探针的发色团。     

MCM-41介孔分子筛负载咔唑类荧光分子杂化材料的合成及发光性质

通过浸渍法将5种咔唑类荧光分子负载于介孔材料MCM-41上,制备有机-无机杂化复合荧光材料,并对咔唑荧光分子和杂化复合材料的表面结构、紫外-可见吸收、荧光发射等性质进行了对比。结果表明,负载后的咔唑类荧光分子分散于MCM-41孔道上,材料热稳定性提高,在100~350℃内没有明显失重,其紫外吸收和荧光发射也发生明显蓝移(λmaxabs=331~368 nm,λmaxem=401~435 nm)。制备的杂化复合材料可用作蓝色荧光材料(λmaxem=401~435 nm)。     

双光子镉离子荧光探针TPCN合成及光谱性质研究

双光子荧光探针具有长波激发、短波发射的特点,可以有效避免样品本底荧光和散射光的干扰,在生物分析中有较多应用.通过Wittig-Horner反应合成了发光机理为分子内电荷转移(ICT)型、分子构型为D-A-D型(A表示电子受体,D表示电子给体)的双光子镉离子荧光探针TPCN.探针随镉离子浓度增加,荧光强度呈线性下降并伴随...     

Fluorescence upconversion properties of a chiral polybinaphthyl induced by two‐photon absorption

The fluorescence properties of a chiral polymer based on optically active polybinaphthyls were studied in tetrahydrofuran solution. One‐photon excited fluorescence of the polymer was located in the range of ～ 596 nm and the corresponding lifetime was ～ 4.38 ns. From the excitation spectra and emission spectra excited at 800 nm, the upconversion fluorescence emission was observed. When excited by using 800 nm fs laser pulses with different input irradiances, the peak fluorescence intensity of the solution provides square dependence with the input irradiance power, giving an evidence for two‐photon excited fluorescence. Furthermore, open aperture Z‐scan measurements were performed at different irradiation intensities to confirm two‐photon absorption property of the solution at 800 nm excitation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Photochemie substituierter Cycloheptatriene. XII. Dualfluoreszenz von 1-Aryl-4-(p-dimethylaminophenyl)-cycloheptatrienen

Photochemistry of Substituted Cycloheptatrienes. XII. Dual Fluorescence of 1-Aryl-4-(p-dimethylaminophenyl)-cycloheptatrienes Diarylcycloheptatrienes 1 in solution show two fluorescences originating from two different excited states. The ratio of intensities of the two fluorescences depends on the excitation energy. Two alternatives are discussed as the origin of the dual fluorescence: conformers in the ground state or an adiabatic photoreaction, respectively. The two emissions are ascribed to different geometries of the seven-membered ring. Despite the different excitation spectra the dual fluorescence of the compounds 1 is explained as an excited state property of a single absorbing species, and not as two ground state species giving rise to the two fluorescence bands.     

The facile synthesis of novel phenothiazine derivatives for blue,yellow-green,and red light emission

Two blue emitters, 3,7-bis(5′-(trifluoromethyl)-1′H-pyrazole-3′-yl)10-ethylphenothiazine and 3,7-bis(5′-(phenyl)-1′H-pyrazole-3′-yl)10-ethyl-phenothiazine and one red, bis-dioxaborine emitter, each based on two, yellow-green emitting, bis-β-diketonate, phenothiazine derivatives, were obtained in high yield and characterized. Systematic investigation of the two-photon absorption characteristics was carried out using one-photon absorption, one-photon excited fluorescence as well as two-photon excited fluorescence spectra. TDDFT computational studies were undertaken to secure an insight into the nature of the compounds' electrochemical and photophysical properties. Low-energy absorption transmissions resemble those observed for the experimental one-photon absorption spectra.     

萘修饰的树枝形聚酰胺-胺的合成与荧光性质研究

在DMF溶剂中使用不同代数的整代树枝形聚合物聚酰胺-胺(PAMAM)与1,8-萘二甲酸酐进行酰胺化反应,制备了1,8-萘酰亚胺修饰的3.0G以及5.0G的树枝形聚合物D3、D5。对产物进行红外、紫外-可见吸收、荧光发射、激发光谱以及元素分析的表征,产物与目标产物结构一致。在氯仿与乙醇(体积比为1∶1)的混合溶剂中,由于PAMAM对萘环的固定作用,在萘环浓度相同的情况下,1,8-萘二甲酸酐不形成激发态萘环与基态萘环的激基缔合物,而聚合物D形成了分子内萘环的激基缔合物,在471 nm处产生萘环激基缔合物的荧光发射峰,具有潜在的应用价值。     

Fluorescence of Gd+++ in Alkali Halide Crystals

Crystals of potassium chloride and potassium bromide containing trivalent gadolinium were prepared from the melt and also by heating the powdered anhydrous mixtures at 600°C. Their fluorescence spectra consisted of four sharp lines around 3114.3 Å and 3115.1 Å respectively. A single mode of charge compensation for the substituted Gd³⁺ ion with a D₃h or C_2v symmetry is proposed. Lifetimes of the fluorescence of these doped crystals as well as of pure GdCl₃ and GdBr_s are of the order of a few msec.     

3-5-二（2＇-芳基-1＇，3＇，4＇-噁二唑基）吡啶荧光光谱的量子化学研究

对3种3-5-二（2＇-芳基-1＇,3＇,4＇-噁二唑基）吡啶的荧光光谱进行了理论研究。采用密度泛函（DFT）方法,在B3LYP／6-31G水平下,对化合物的几何构型进行了全参数优化。经振动分析,均未出现虚频率。在此基础上,采用组态相互作用（CI）方法计算了荧光激发光谱,所得结果与实验值基本吻合。计算结果表明,三种分子具有较强的共面性,为超共轭体系。     

Resonance raman spectroscopy of polydiacetylene langmuir-blodgett films

Resonance Raman excitation profiles of two vibrational modes have been measured for Langmuir-Blodgett films of a polydiacetylene. The polymer films were formed by exposing multilayer samples of the Cd salt of 10,12-pentacosadiynoic acid to ultraviolet radiation. Raman spectra were measured for incident laser photon energies between 1.85 and 2.20 eV (670-564 nm), the region over which the films exhibited optical absorption associated with an electronic transition of the π-electrons on the conjugated backbone. The excitation profiles have been used to determine both the strength of the vibronic coupling and the differences in vibrational frequency between the ground and excited states. The results are in reasonable agreement with those obtained previously for polydiacetylene single crystals.     

稀土铽络合物在油墨中的应用性能

合成了3个稀土铽与1-苯基-3-甲基-4-酰基吡唑啉酮-5的络合物,用红外光谱、紫外吸收和元素分析表征了它们的结构.将这3个铽络合物固体作为隐形荧光颜料配制成油墨,测试了油墨印品的荧光性能以及各项牢度.结果表明这3种油墨印品在254 nm紫外波长的激发下发光强度高,其中以1-苯基-3-甲基-4-乙酰基吡唑啉酮-5和1-苯基-3-甲基-4-丙酰基吡唑啉酮-5为配体的两种铽络合物在油墨中耐碱、次氯酸钠、甲苯、四氯乙烯、汽油的牢度优良.     

Absorption and Fluorescence Spectra of Nitrobenzanthrones

To identify nitrobenzanthrones (NBAs) such as 3-nitro-7 H -benz[ de ]anthracene-7-one (3-NBA) on the basis of their electronic spectral data, we have synthesized 1-, 2-, 3-, 9-, and 10-NBAs and measured their absorption and emission spectra. The first strong absorption band of the NBAs appeared in the region 350-440 nm; the band of 10-NBA was red-shifted by about 20 nm. The molar absorptivities of 3- and 9-NBA were about two times as large as those of the others. The fluorescence spectra of the NBAs varied more largely with the position of the nitro group compared to the absorption spectra. The quantum yields of fluorescence were very small, ranging from ～10 m 2 for 2- and 10-NBA to ～10 m 4 for 1- and 3-NBA. 3-NBA exhibited a characteristic spectrum with two broad bands at 450 and 530 nm. On excitation causing an n ~ * transition in the NBAs, their fluorescence intensities increased by a factor of 10. Phosphorescence was observed at 77 K for all compounds though that of 1-NBA was very weak. These results give the promise of characterizing individual isomers of NBAs on the basis of their spectroscopic data.     

含有均二苯乙烯基的苯并二口恶唑衍生物的合成及荧光特性

引言 目前人们已发现许多均二苯乙烯衍生物具有蓝色发光的特性[1-2],此类有机共轭小分子作为空穴型光电发光材料的共轭化学结构已确定并且发光色度纯,两个苯环上引入取代基对其发光波长和光量子效率还有调节作用,合成方法也比较简单[3-4].