2, 6-双(2-苯并咪唑)吡啶-乙酸锌的合成和光谱性能

合成了一种新型的蓝光发射材料2,6-双(2-苯并咪唑)吡啶-乙酸锌,并利用元素分析、红外光谱、UV-Vis吸收谱、荧光激发光谱和荧光发射光谱研究了其结构、光学特性、能级结构和发光机理。结果表明,2,6-双(2-苯并咪唑)吡啶-乙酸锌是一种三齿配体的发光材料。在N,N-二甲基甲酰胺(DMF)溶液体系中测定了材料的紫外吸收光谱,2,6-双(2-苯并咪唑)吡啶的吸收峰波长主要为330,344nm;2,6-双(2-苯并咪唑)吡啶-乙酸锌的吸收峰波长主要为346,366nm。禁带宽度为3.01eV,在紫外光激发下,在DMF溶液体系中的荧光发射峰在458nm处,固态荧光发射峰在475nm,均为蓝色荧光,色纯度高,荧光量子效率高,其荧光发射主要来源于长波吸收带,最大波长吸收带对荧光发射贡献最大。有望通过合理的设计运用到有机电致发光器件中去。     

两种新型芴衍生物的合成、晶体结构及光谱性能

合成了两种新型芴衍生物:2,7-二（3,5-二（三氟甲基）苯基）-9,9-二乙基芴（1）和2,7-二（4-氟苯基）-9,9-二乙基芴（2）。通过元素分析、红外光谱（IR）、核磁共振氢谱（¹H NMR）以及单晶X射线衍射对其结构进行了表征。化合物1属于单斜晶系,P2₁/c空间群;化合物2属于三斜晶系,P-1空间群。通过紫外-可见吸收和荧光光谱研究了化合物的发光性能。结果表明:在CH₂Cl₂溶液和固态薄膜中,化合物1、2在350～400 nm波段有吸收峰,归属于π-π^*电荷跃迁;化合物1、2的光学带隙E_g分别为3.31 eV和3.30 eV,并且均有强烈的蓝色荧光发射现象（激发波长为330 nm）,在二氯甲烷中的荧光量子效率分别为0.62和0.61,固态荧光寿命分别为6.39 ns和9.00 ns。     

A new coumarin laser dye 3-(benzothiazol-2-yl)-7-hydroxycoumarin

The electronic absorption, and emission spectra as well as fluorescence quantum yield of 3-(benzothiazol-2-yl)-7-hydroxycoumarin (BTHC) were measured in different solvents and are affected by solvent polarity (Δf). The deprotonation of BTHC by triethylamine is a reversible process. BTHC is relatively photostable, the quantum yield of photodecomposition (φ_c) was found to be 2×10⁻⁴ and 2.7×10⁻⁴ in EtOH and DMF, respectively. The fluorescence lifetimes of BTHC were measured in the absence and in the presence of molecular oxygen and were found to be 2.82 and 2.78 ns, respectively. BTHC acts as good laser dye upon pumping with nitrogen laser (λ_ex=337.1 nm) in ethanol and gives laser emission with maxima at 508 and 522 nm.     

2(水杨醛缩苯胺)-(1,10-邻菲罗啉)合钙的光谱特性

合成了一种新型的蓝光发射材料2(水杨醛缩苯胺)-(1,10-邻菲罗啉)合钙,并利用红外光谱、X射线衍射谱、DSC热分析、UV-vis吸收谱、荧光激发光谱和荧光发射光谱研究了其结构、晶态、热稳定性以及光学特性,分析了它的能态结构和发光机理。结果表明,2(水杨醛缩苯胺)-(1,10-邻菲罗啉)合钙的热稳定性较高,是一种多晶粉末发光材料,禁带宽度2.93eV,在紫外光的激发下,固态荧光发射峰在449.7nm处,在乙醇溶液体系中的荧光发射峰在491nm处,均为蓝色荧光,色纯度高,荧光量子效率高,其荧光发射主要来源于长波吸收带,最大波长吸收带对荧光发射贡献最大。     

Photophysical Properties of some 1,3,4-Oxadiazole Derivatives Containing Phenolphtalein,Fluorene and Bisphenol A Units

The photophysical properties of the three 1,3,4-oxadiazole derivatives containing fluorene (Ox-FL); fluorene and phenolphtaleine (Ox-FL-FF); or fluorene and bisphenol A (Ox-FL-BPA) moieties in the main chain were investigated by the fluorescence and absorption spectroscopy in different solvents and in the solid state. The electronic absorption spectra included a strong absorption band located in the 270–395 nm region, with a maxima around at 302 nm. The fluorescence excitation spectra were also characterized by one broad band, appearing in the wavelength range of 220–340 nm. All samples displayed the emission bands around 356–373 nm and exhibit high quantum yields ranged from 31.61 to 90.77%, in chloroform solution. The sensitivity of the emission spectra on medium characteristics (polarity, acidity and basicity) were evaluated by using the Catalan solvent scale and the fluorescence titration with a dilute acid solution.     

Analysis of branched oligophenylene by absorption and fluorescence spectra

A branched oligophenylene has been synthesized based on 1,3,5-tri(4′-bromophenyl)benzene. Absorption and fluorescence spectra were studied and fluorescence quantum yields and lifetimes were measured for the compound in solution. It is demonstrated that the absorption spectrum is a superposition of p-quaterphenyl, p-terphenyl, and biphenyl chromophore absorption bands in a 1:2:1 ratio. The oligomer fluorescence spectrum is found to depend on the excitation wavelength. It is shown that the oligomer fluorescence is determined by two fluorochromic groups, namely fragments with branched p-terphenyl and p-quaterphenyl units. The main fluorescence maxima for these fluorochromic groups coincide with each other and lie in the vicinity of λ = 360 nm. A very weak fluorescence band found in the region 380–440 nm is excited by light with a wavelength lying beyond the oligomer self-absorption region. The reasons for a decrease in fluorescence quantum yields of branched models and the studied oligophenylene as compared with those of linear p-polyphenylene chromophores are discussed.     

2(8-羟基喹啉)-2(苯酚)合锆薄膜的制备与性能研究

设计合成了一种新型的有机电致发光材料2(8-羟基喹啉)-2(苯酚)合锆(Zr(OPh)₂q₂),制备了Zr(OPh)₂q₂薄膜,并利用红外光谱、差热-热重谱、扫描电镜、X射线衍射谱、UV吸收谱和荧光光谱等方法研究了其晶态、热稳定性、能带结构以及光致发光机理。结果表明,Zr(OPh)₂q₂的熔点为381.2 ℃,分解温度为467.1 ℃,具有非常高的热稳定性,利用真空热蒸镀方法很容易在经过净化处理的玻璃基底上形成高质量、无定形纳米级薄膜,在390 nm紫外光的激发下,Zr(OPh)₂q₂薄膜产生发光峰为525 nm、半峰宽度为107.6 nm的强黄绿色荧光,其粉体产生强黄色荧光,是一种性能优良的电致发光材料。     

有机电致发光器件中新型芴类小分子材料的光谱特性

针对新型芴类小分子材料6,6′-(9H-fluoren-9,9-diyl)bis(2,3-bis (9,9-dihexyl-9H-fluoren-2-yl) quinoxaline) (BFLBBFLYQ)和空穴传输材料N,N′-biphenyl-N,N′-bis-(3-methylphenyl)-1, 1′-biphenyl-4,4′-diamine(TPD)及二者混合体系的荧光光谱和吸收光谱进行了测试表征,制备了结构为indium-tin oxide (ITO)/BFLBBFLYQ∶TPD/Alq/Mg∶Ag的双层有机电致发光器件。研究发现,BFLBBFLYQ∶TPD混合薄膜存在一个不同于单独分子薄膜的低能量发射光谱,发光峰在530 nm处,与tris(8-hydroxyquinolinato)aluminum(Alq)薄膜的荧光光谱相同,亦与结构为BFLBBFLYQ∶TPD/Alq双层器件的电致发光光谱相同。鉴于荧光染料4-(dicyanomethylene)-2-tert-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl) -4H-pyran(DCJTB)的吸收光谱与Alq的荧光光谱有很好的重叠,利用Forster能量传递理论,将DCJTB红色染料引入双层器件,通过调节掺杂位置,考察器件的发光光谱情况,进而对BFLBBFLYQ∶TPD/Alq双层器件的载流子复合区域进行了研究。结果表明,双层器件的载流子复合区域位于BFLBBFLYQ∶TPD/Alq界面附近的Alq层内。     

黄烷酮及其羟基衍生物的荧光性质研究

黄烷酮类化合物是天然药物的重要活性成分,也是有机合成的研究热点之一,但此类化合物的荧光性质尚缺乏研究。研究了黄烷酮及其6种羟基衍生物的荧光性质,发现黄烷酮(Flavanone,FV)、7-羟基黄烷酮(7-Hydroxyflavanone,7HF)和6-羟基黄烷酮(6-Hydroxyflavanone,6HF)的水溶液有荧光,而2’-羟基黄烷酮(2’-Hydroxyflavanone,2’HF)、4’-羟基黄烷酮(4’-Hydroxyflavanone,4’HF)、柚皮素(4’,5,7-三羟基黄烷酮,Naringenin)和乔松素(5,7-二羟基黄烷酮,Pinocembrin)的水溶液基本无荧光。在三维荧光图谱中,FV的荧光激发波长(λ_ex)为235,265和340 nm,发射波长(λ_em)为386 nm;7HF的λ_ex为230,276和315 nm,λ_em为391 nm;6HF的λ_ex为260和356 nm,λ_em为482 nm。研究了pH对FV,7HF和6HF荧光的影响,从分子结构的角度讨论了pH对荧光产生影响的原因。研究了7HF和6HF在不同pH条件下的紫外吸收光谱,用pH-光度法测得7HF和6HF的羟基质子电离常数pK_a分别为7.26±0.05和9.90±0.02。研究了溶剂(甲醇)对FV,7HF和6HF荧光光谱的影响,发现FV和7HF在甲醇溶液中的荧光比在水中减弱,而6HF在甲醇中的荧光显著增强。在有序介质(SDS,CTAB,β-CD)中,FV和7HF的荧光减弱,而6HF在β-CD或CTAB中的荧光增强。以硫酸奎宁或L-色氨酸为参比,测得FV和7HF水溶液的荧光量子产率分别为0.057和0.012;6HF在甲醇中和在β-CD浓度为1.62 mg·mL-1的水溶液中的荧光量子产率分别为0.064和0.012。     

4,6-二甲氧基-2-嘧啶氨基甲酸甲酯分子结构与光谱

运用密度泛函理论B3LYP方法,6-311G*和6-311 G*基函数对4,6-二甲氧基-2-嘧啶氨基甲酸甲酯分子结构与光谱性质进行理论研究,得到分子的平衡结构参数和最大吸收波长.4,6-二甲氧基-2-嘧啶氨基甲酸甲酯分子具有Cs对称性和较大的前线轨道能隙值.基函数对计算结果无影响.     

Luminescence of Molecules with Internal Charge Transfer upon Longwave Excitation

We have studied the spectral properties of luminescence of laurdan molecules in glycerin upon excitation at the red edge of the absorption band at different temperatures. The most significant red-wave shift of the spectra (10 nm) for the longwave band of dual fluorescence is observed depending on the excitation wavelength at a low temperature of 260 K when a solvent forms a fairly rigid matrix. At the same time, at increased temperatures of up to 370 K a small bathochromic shift and a change in the shape of the luminescence bands are also recorded reliably. Changes in the excitation spectra were observed when luminescence was recorded in the bands of the LE- and CT states. The difference spectrum responsible for the additional absorption that does not make a contribution to the longwave luminescence component has been isolated. The decay kinetics of both luminescence components have been measured and their expansions in decay constants have been analyzed. The experimental dependences obtained point to the complex mechanism of inhomogeneous broadening of spectra.     

一种9-苯基芴位阻功能化的苯胺中间体的设计合成、表征及其光电性质

以醋酸为溶剂、浓硫酸为催化剂在120 ℃回流24 h, 通过傅克反应设计合成了一种大体积位阻型9,9-二芳基芴中间体[9-(4-苯胺基)-9-苯基芴](FPPhNH₂)。通过核磁氢谱、质谱、红外等方法对该化合物的分子结构进行了详细表征。核磁氢谱和红外光谱分别在6.55 ppm,3 481和3 385 cm-1显示该化合物的特征官能团-氨基。用紫外-可见光谱和荧光光谱对9-(4-苯胺基)-9-苯基芴的光学性质进行了表征和初步探讨。研究结果表明, 具有大体积空间位阻效应的9-(4-苯胺基)-9-苯基芴在二氯甲烷溶液中有四个主要吸收峰, 其吸收波长分别为243,257,298和311 nm; 在波长为308 nm的谱激发下,得到发射波长为300～500 nm的发射光谱曲线, 其荧光光谱最大发射波长为328 nm, 且在405 nm左右有一个细小的峰并有一个长的拖尾至500 nm, 这可能源于苯胺基团中分子间氢键所引起的。恰当的荧光发射范围(300～500 nm), 使其能够和经典蓝光客体材料双(4,6-二氟基吡啶-N,C2)吡啶甲酰合铱(FIrpic)的吸收光谱有较大的重叠(300～500 nm)。通过巧妙的分子裁剪, 或可得性能优异的主体材料, 进而使制备高性能的发光器件成为可能。为了进一步了解该化合物的光电性能, 以乙腈为溶剂, 以四丁基六氟磷酸胺为电解质, 通过循环伏安法对该化合物的电化学性能进行了表征。其起始氧化电位和还原电位分别为0.898和-0.759 V, HOMO和LUMO能级分别为-5.38和-3.72 eV, 其较高的HOMO能级和较低的LUMO能级有利于空穴和电子的注入/传输, 这将进一步优化成性能优异的主体材料, 并为进一步制备性能优异的有机半导体发光器件提供有益参考。     

Cu2O半导体超微粒子的光学性质

本文研究了表面修饰的Cu2O半导体超微粒子的光学性质.在Cu2O超微粒子中未观察到显著的量子尺寸效应,但测量到很强的宽带光致发光,且随着激发波长变短,其发光带的峰位蓝移,发光带宽度增加.最后,分析了Cu2O超微粒子的宽带发光机制,并讨论了热处理对超微粒子的发光强度的影响.     

Singlet Oxygen Quantum Yield Determination for a Fluorene-Based Two-Photon Photosensitizer

The quantum yield, Φ_Δ, of singlet oxygen generation under two-photon excitation has been determined for a fluorene derivative. A photochemical method was developed using 1,3-diphenylisobenzofuran (DPBF), a chemical quencher of ¹O₂, and 2-(9,9-didecyl-7-nitrofluoren-2-yl)benzothiazole (1) as a two-photon photosensitizer (PS). The photochemical kinetics of the quencher was measured by two different fluorescence methods. Fluorene 1 exhibited relatively high singlet oxygen quantum yield, Φ_Δ ≈ 0.4 ± 0.1, and had a two-photon absorption cross-section of 28 ± 5 GM. Thus, 1 may have potential for use as a two-photon PS in the near-IR spectral region for biomedical applications.     

(S)-N-苄基-2-吡咯烷-α,α-二苯基甲醇的荧光光谱与荧光量子产率

研究了溶剂、酸度、表面活性剂以及温度对(S)-N-苄基-2-吡咯烷-α,α-二苯基甲醇(BPPE)荧光光谱的影响。以L-酪氨酸为参比,测量了BPPE乙醇溶液在不同波长下的荧光量子产率,在最大激发波长245nm下,BPPE的荧光量子产率为0.155。     

磺基水杨酸的荧光光谱与荧光量子产率

报道了磺基水杨酸 (SSA)的荧光光谱和荧光量子产率。在 pH <2时 ,SSA无荧光 ,随pH升高 ,SSA荧光增强 ,在 pH 5～ 10 5之间 ,SSA有稳定的强荧光 ,最大发射波长为 4 0 2nm ,激发波长为 2 12 ,2 38和2 97nm。在 pH >13的强碱性条件下 ,SSA转变为另一种荧光型体 ,最大激发波长 2 6 1nm ,最大发射波长390nm。SSA浓度较高时 ,荧光激发光谱发生变化 ,但发射光谱不变。在近中性条件下 ,SSA稀溶液的荧光强度与浓度之间存在良好的线性关系 ,线性范围为 5～ 2 5 0ng·mL- 1 ,检测下限为 5ng·mL- 1 。以硫酸奎宁为参比 ,测量了SSA在不同波长下的荧光量子产率 ,在最大激发波长 2 97nm处的荧光量子产率为 0 5 4。     

Spectroscopic and travelling-wave lasing characterisation of tetraphenylbenzidine and di-naphtalenyl-diphenylbenzidine

The organic light emitting diode (OLED) hole transport molecules N,N,N’,N’-tetraphenylbenzidine (TPB, triphenylamine dimer TAD or TPD) and N,N’-bis(2-naphtalenyl)-N,N’-bis(phenylbenzidine) (β-NPB, naphtyl-diphenylamine dimer β-NPD), dissolved in tetrahydrofuran (THF) and as neat film, are characterized by optical absorption and emission spectroscopy. The absorption and stimulated emission cross-section spectra, the fluorescence quantum distributions, fluorescence quantum yields, degrees of fluorescence polarization, and fluorescence lifetimes are determined. The lasing behaviour is studied by picosecond laser pulse excitation (excitation wavelength 347.15 nm, pulse duration 35 ps). The excited-state absorption at the pump laser wavelength is determined by saturable absorption measurement. Low-Q laser oscillation of TPB in THF is achieved by transverse pumping of the dye in a cell. The excited-state absorption of TPB in THF at the laser wavelength is extracted from the laser threshold. In TPB neat films, wave-guided travelling-wave lasing was obtained. No laser action was achieved for β-NPB because of small S₁-S₀ stimulated emission cross-section, and the presence of excited-state absorption in the fluorescence wavelength region. The TPB and β-NPB results are compared with the corresponding spectroscopic and lasing behaviour of the related methyl-substituted triphenylamine dimers, 3-methyl-TPD and 4-methyl-TPD, which are well established OLED hole transport materials.     

Theoretical modelling of encapsulation of the Altretamine drug into BN(9,9-5) and AlN(9,9-5) nano rings: a DFT study

The aim of this paper is a better comprehension of the encapsulation and interaction an anticancer drug Altretamine into BN nano ring [BNNR(9,9-5)] and AlN nano ring [AlNNR(9,9-5)]. The electronic and adsorption properties of the molecule Altretamine over the BNNR and AlNNR were theoretically studied in the solvent phase at the B3LYP/6-31G* level of theory for the first time. With the non-bonded interaction of Altretamine, the electronic properties of the BN and AlN nano-cages can be significantly changed. The electronic spectra of the Altretamine drug, complex BNNR/Altretamine and AlNNR/Altretamine in solvent water were calculated by Time Dependent Density Functional Theory (TD-DFT) for the investigation of adsorption effect. According to the natural bond orbital (NBO) results, the molecule Altretamine, BNNR and AlNNR play as both electron donor and acceptor at the complexes BNNR/Altretamine and AlNNR/Altretamine. On the other hand, the charge transfer is occurred between the bonding, antibonding or nonbonding orbitals in the molecule drug, BNNR and AlNNR. As a consequence, BNNR(9,9-5) and AlNNR(9,9-5) can be considered as a drug delivery system for the transportation of Altretamine as anticancer drug within the biological systems.     

金纳米粒子掺杂DNA-CTMA-DPFP薄膜的表面增强拉曼散射特性

采用柠檬酸三钠还原氯金酸和离子交换法制备金纳米粒子掺杂DNA-CTMA材料,利用钯催化反应合成9,9-二乙基-2,7-二-(4-吡啶)芴荧光染料(DPFP),将DPFP与DNA-CTMA混合后,旋凃制备金纳米粒子掺杂的DNA-CTMA-DPFP薄膜样品。通过吸收光谱、荧光光谱和拉曼光谱的测量,研究了薄膜样品的光学特性和表面增强拉曼散射(SERS)特性。实验结果表明,薄膜样品在300～360 nm的吸收主要来自DPFP,在500～700 nm的吸收来自样品中金纳米粒子的局域表面等离子共振;样品在370,386,408 nm处的荧光峰分别对应DPFP的S₁₀-S₀₀、S₁₀-S₀₁和S₁₀-S₀₂能级的电子振动跃迁;在785 nm激光激发下,薄膜样品的拉曼散射主要来自DPFP分子,随着金纳米粒子掺杂比的增大,DPFP分子的拉曼散射峰强度逐渐增强。因此,金纳米粒子掺杂DNA-CTMA薄膜适合作为多种染料分子的SERS基底。     

Polarized Fluorescence of Diphenylhexatriene-Incorporated Poly(Styrene) Film at Room Temperature

Poly(styrene) is a highly viscous, and cross-linked polymer at room temperature. This makes it ideal to use as a molecular fixer. The polarized fluorescence of a diphenylhexatriene (DPH)-incorporated poly(styrene) film has been studied. The excitation and emission wavelength dependence of the anisotropy of fluorescence of a luminophore-incorporated poly(styrene) film reveals that with decreasing excitation wavelength the anisotropy changes remarkably but is independent of emission wavelength. The investigation estimates an angle of no more than 7.4° between the absorption and the emission transition dipole moment for DPH, suggesting poly(styrene) as a suitable medium to evaluate the mutual orientation of absorption and the emission transition dipole moments at room temperature.