磷光配体3-[4-(2-吡啶基)苯基]-9-(4-氟苯基)-9H-咔唑的合成

以对溴苯胺为原料,经重氮化、Gomberg-Bachmann偶联、硼酸化反应得到4-(2-吡啶基)苯硼酸;再与对氟苯基取代的咔唑,通过四(三苯基磷)钯催化,于90℃进行Suzuki偶联合成出标题磷光配体,收率82.03%。对目标物用核磁共振氢谱和元素分析进行了表征,并测得它在二氯甲烷中的紫外吸收光谱和荧光光谱。由于受咔唑基团的影响,磷光配体最大吸收峰波长红移56 nm,且吸收的强度增加,Stokes位移154 nm,相对荧光量子效率为0.17。     

新型黄光铱磷光配合物的合成、表征及性能研究

通过在2,4-二氯吡啶上引入3-联苯基,合成了一种以2,4-二(3-联苯)吡啶为主配体,以2,2,6,6-四甲基-3,5-庚二酮为辅助配体的新型有机电致磷光材料,通过元素分析、红外光谱、~1H NMR和质谱对产物进行了结构表征,利用X射线单晶衍射仪测定了配合物的晶体结构。并对其用紫外-可见吸收、光致发光、热稳定性等进行研究。研究表明,配合物在395和465nm处存在单重态~1MLCT(金属到配体的电荷跃迁)和三重态~3MLCT的吸收峰;其初始分解温度为405℃(对应于10%质量损失),最大发射波长为570nm,是一种可用于白色有机电致发光器件的新型黄色发光磷光材料。     

一种绿色铱磷光配合物的合成及性能研究

以3-苯基苯硼酸、2-溴吡啶为原料,通过与三氯化铱的配合反应,合成了一种绿色有机电致磷光材料[二(2-联苯基吡啶)](2-吡啶甲酸)合铱(Ir(bppy)2pic),通过1H NMR、质谱对其进行了结构表征。并对配合物的紫外吸收和发光性能进行考察,研究表明其在405 nm和475 nm处存在单重态1MLCT和三重态3MLCT的吸收峰;最大发射波长为503 nm,是一种具有更加饱和的发射光谱的绿色磷光材料。     

基于三苯胺的D-A-π-A-D型化合物的合成及光物理性能

以甲氧基三苯胺为电子供体,苯并噻二唑为电子受体,咔唑为共轭π桥,通过三步Suzuki偶联反应合成了D-A-π-A-D型荧光化合物4,4′-[(7,7′-9 H-咔唑-2,7-)-二(苯并噻二唑-7,4-)]-二(N,N-二(4-甲氧基苯基))苯胺(DTB-CZ),并用1HNMR、¹³CNMR、MALDI-TOF等手段对其结构进行表征。研究了它的光谱性能、电化学性能、轨道能级和热性能,并与D-π-D型化合物2TPA-CZ1的性能进行了比较。初步探索了DTB-CZ作为空穴传输材料在PSC中的应用。研究结果表明,DTB-CZ在甲苯溶液中的最大吸收波长为479 nm,最大发射波长为608 nm,在薄膜状态下最大吸收波长为495 nm,HOMO/LUMO能级为-4.91/-2.82 eV,带隙值为2.09 eV,热分解温度(T_5d)为449.6℃,玻璃化转变温度(T_g)为143.1℃。相比2TPA-CZ1,在甲苯溶液中吸收和发射波长分别红移了104、182 nm,在薄膜状态下吸收波长红移109 nm;带隙值降低0.84 eV;T 5d和T g分别提高了9.6、24.7℃。结果表明,苯并噻二唑的引入,使化合物的共轭程度增大,带隙值降低,使得吸收和发射波长红移,使其具有更好的热稳定性和形态稳定性。     

β-二酮类铱配合物的合成、表征及光电性能

以5-甲基-2-苯基吡啶(CH3ppy)为主配体,3,7-二乙基-4,6-壬二酮(detd)、2,2,6,6-四甲基-3,5-庚二酮(tmd)和乙酰丙酮(acac)为辅助配体(LX),设计合成了3种含β-二酮类辅助配体的绿色磷光金属铱配合物(Ⅲ、Ⅳ、Ⅴ)。通过1HNMR和元素分析对其结构进行了表征,通过UV-Vis光谱和荧光发射光谱(PL)测得化合物Ⅲ、Ⅳ、Ⅴ的最大吸收波长范围在250～280 nm,最大发射波长分别为530.8、534.2和524.8 nm。制备了3种有机发光二极管(OLEDs)。结果表明,以化合物Ⅲ制备的器件亮度可以达到59125 cd/m2,最大外量子效率为15.0%,最大电流效率为53.8 cd/A,最大功率效率为62.1 lm/W,色坐标(0.30,0.62),在3个器件中综合性能表现最好。     

噻吩基与苯基修饰的铱(Ⅲ)配合物合成与光谱性质对比

本研究将传统的2-苯基吡啶配体进行改性,用富电子的噻吩基团代替苯基,得到有机配体2-噻吩基吡啶(L1),并以L1合成铱(Ⅲ)配合物C1,而基于2-苯基吡啶(L2)配体的铱(Ⅲ)配合物C2也被合成得到,以用做性质对比;随后通过质谱(MS)、核磁共振谱(NMR)以及傅里叶变换红外光谱(FT-IR)对产物C1和C2进行结构表征,并利用紫外可见光吸收光谱(UV-Vis)以及光致发光光谱(PL)等测试手段,对比C1与C2的光谱性质,利用噻吩基代替苯基后,UV-Vis的吸收范围扩大,PL的最大发射峰发生了红移。     

香豆素类化合物的合成及其光谱性质的研究

本文分别用Wittig反应、Perkin反应和Pechmanmn反应合成了邻甲氧基取代二苯乙烯及其由内酯键固环为3-位苯环或4-位苯环取代的香豆素化合物，固环为3-位苯环取代的香豆素化合物的最大吸收波长稍有红移约2nm，而发射波长产生了约20nm的较大红移，Stokes位移增大了18nm，荧光量子效率也稍有提高。香豆素化合物在7-位由供电基甲氧基取代后，最大吸收波长红移16nm，发射波长红移21nm，Stokes位移增大5nm，荧光量子效率却提高了近四倍，荧光量子效率接近1．0。7-位同为甲免基取代，由3-位对溴苯基变为4-位对溴苯基取代时，吸收波长蓝移16nnn，荧光发射波长亦蓝移20nm，Scokes位移降低4nm，荧光量子效率大幅度降低。     

β-四(4-咪唑基苯基)亚氨酞菁锌的合成及光电性能研究

通过4-硝基邻苯二甲腈先成环,后修饰的合成步骤,得到对咪唑苯甲醛与酞菁环通过希夫碱基团直接桥连的β-四(4-咪唑基苯基)亚氨酞菁锌(SPc)。通过红外光谱、核磁共振氢谱表征了其结构,进行了紫外可见光和荧光光谱测试。研究发现SPc在吡啶中溶解性最好,在一定的浓度范围之内,SPc分子间没有聚集行为,摩尔吸光系数与浓度成正比。SPc在DMF溶液中紫外-可见光吸收峰Q带位于693 nm,与无取代酞菁锌相比,Q带红移了26 nm。445 nm激发波长下,荧光发射波长为560 nm。     

一种铱磷光配合物的合成表征及性能研究

利用2-苯基吡啶(ppy)、三水合氯化铱(IrCl_3·3H_2O)和2-吡啶甲酸(pic)配位,得到铱配位物Ir(ppy)_2pic,合成产率9 0%,该方法适合于Ir(ppy)2pic的批量制备。通过元素分析、核磁共振(~1H-NMR、~(13)C-NMR)和质谱(MS)对产物分子结构进行了表征,此外结合紫外吸收光谱(UV-Vis)和荧光光谱(PL)对其光物理性能进行了研究。结果表明:该配合物在紫外谱图上的250~300 nm处出现了强的配体单重态π-π*自旋跃迁吸收峰,在400~500 nm处出现了铱(Ш)到配体的单重态和三重态(~1MLCT和~3MLCT)电子跃迁吸收峰,在荧光光谱的514 nm处有较强的金属配合物三重态的磷光发射峰,显示为一种高效的绿色磷光材料。     

β-二酮类铱配合物的合成、表征及光电性能测试

以5-甲基-2-苯基吡啶（CH3ppy）为主配体，3,7-二乙基-4,6-壬二酮（detd）、2,2,6,6-四甲基-3，5-庚二酮（tmd）和乙酰丙酮（acac）为辅助配体（LX），设计合成了三种含-二酮类辅助配体的绿色磷光金属铱配合物（Ⅲ,Ⅳ,Ⅴ）。通过1HNMR和元素分析对其结构进行了表征，通过UV-vis光谱和荧光发射光谱（PL）测得化合物Ⅲ、IV、V的最大吸收波长范围在250 nm~280 nm之间，最大发射波长分别为530.8 nm、534.2 nm和524.8 nm。制备了器件结构为：ITO/HAT-CN (15nm)/TAPC (50nm)/TCTA (5nm)/TCTA:X (8%,15 nm)/Bepp2 (35nm)/LiF (1nm)/Al (150nm)的有机发光二极管（OLEDs）。结果表明，以化合物Ⅲ制备的器件亮度可以达到59125.2 cd/m2，最大外量子效率为15.0%，最大电流效率为53.8 cd/A，最大功率效率为62.1 lm/W，色坐标（0.30，0.62），是三个器件中综合性能最好的。     

邻苯二甲酰亚胺衍生物的紫外光谱研究

本文对3个系列，20个邻苯二甲酰亚胺衍生物的紫外光谱进行了测定和分析，发现了其中的取代基效应，并对该结果进行了理论解释。在苯环上取代均使λmax红移，供电能力越强红移越大。     

吖啶橙受溶液pH和浓度变化的光谱研究

利用荧光光谱分析仪研究吖啶橙受溶液pH和浓度变化的吸收光谱和荧光光谱的变化。实验表明,当改变吖啶橙溶液pH和浓度时,它的吸收光谱和荧光光谱发生位移。吖啶橙为1×10-6mol/L时,不同pH的吖啶橙溶液均在(490±3)nm出现一个强吸收峰,pH=6.5,吸收光谱的λm ax=430 nm,发生蓝移;而荧光光谱的λm ax随pH增大发生红移,荧光强度减弱。在浓吖啶橙溶液中,不同pH的吖啶橙溶液的吸收光谱的形状基本相同,出现两个吸收峰,λm ax1分别为(455±3)nm和(430±3)nm,λm ax2分别为(505±4)nm和(510±2)nm,吸收光谱红移;荧光光谱的λm ax均为(535±2)nm,荧光强度荧光很弱。pH相同或相近时,吖啶橙溶液的吸收光谱蓝移和荧光光谱红移,浓度越大,荧光强度越弱。还探讨了吖啶橙在水溶液中的赋存状态,结果表明,在稀溶液中,吖啶橙主要以单体的形式存在;在高浓度吖啶橙溶液中则以吖啶橙单体、二聚体,甚至多聚体形式存在。这说明溶液pH主要影响到吖啶橙分子基态的质子化和氢键的形成能力,使得分子的基态与激发态之间的能量间隔发生了变化,吖啶橙被质子化,则引起发光光谱向短波方向移动,而离解作用,则引起发光光谱向长波方向移动;吖啶橙浓度变化影响吖啶橙在水溶液赋存状态,引起吸收光谱向短波方向移动或向长波方向移动。     

The effect of the diphenylamino side group on the reduction of the molecular interaction between polyurethane copolymer chains

Polyurethane (PU) with a diphenylamino side group is tested for low temperature flexibility at ?30°C and compared with a linear PU without the diphenylamino side group. The PU is composed of 4,4′‐methylenebis(phenylisocyanate) (MDI), poly(tetramethyleneglycol) (PTMG), 1,4‐butanediol (BD), and the diphenylamino group that is grafted to PU chains by a second MDI. The mechanical and shape memory properties of these two types of PU, which differ in the PTMG and the diphenylamino group content, are compared. In the best case, a 306% increase in the maximum stress compared with the linear polymer is attained with a little decrease in the strain. Shape recovery at 45°C increases to 94% and remains ～90% after four cyclic tests. Low temperature flexibility can be improved by increasing the diphenylamino content. The PU with a diphenylamino side group demonstrates the low temperature flexibility at ?30°C, whereas the linear PU must be warmed to room temperature to attain the same degree of flexibility. The exceptional low temperature flexibility is analyzed and is discussed together with the experimental data. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The influence of the region between residues 220 and 344 and beyond in Phrixotrix railroad worm luciferases green and red bioluminescence

To find the regions having a major influence on the bioluminescence spectra of railroad worm luciferases, we constructed new chimeric luciferases switching the fragments from residues 1-219 and from 220-545 between Phrixotrix viviani (PxvGR; lambda(max) = 548 nm) green light-emitting luciferase and Phrixothrix hirtus (PxhRE; lambda(max) = 623 nm) red light-emitting luciferases. The emission spectrum (lambda(max) = 571 nm) and K(M) for luciferin in the chimera PxRE220GR (1-219, PxhRE; 220-545, PxvGR) suggested that the region above residue 220 of PxvGR had a major effect on the active site. However, switching the sequence between the residues 220-344 from PxvGR luciferase into PxhRE (PxREGRRE) luciferase resulted in red light emission (lambda(max) = 603 nm), indicating that the region 220-344 by itself does not determine the emission spectrum. Furthermore, the sequence before residue 220 of the green-emitting luciferase is incompatible for light emission with the sequence above residue 220 of PxhRE. These results suggest that the fragments before and after residue 220, which correspond to distinct subdomains, may fold differently in the green- and red-emitting luciferases, affecting the active site conformation.     

磺化金属酞菁的溶剂效应

文章测试了5种磺化金属酞菁在7种不同极性溶剂中的吸收光谱,用N icol理论研究了金属酞菁染料的溶剂效应。实验和理论结果表明,此类化合物最大吸收峰的波数与函数f(n,ε)存在良好的线性关系,线性相关系数都在0.93以上;而Bayliss函数项(n2-1)/(2n2+1)决定了最大吸收波长(λm ax)的位移变化,λm ax总体上随着溶剂折射率的增大而蓝移,随着溶剂极性的增强而红移。基于此结果,提出了通过选择合适的溶剂调节酞菁染料吸收峰的有效方法,从而使酞菁染料更好地应用于激光防护。     

聚(3-辛基噻吩)的溶致变色、热致变色及发光性能

采用三氯化铁法合成了聚(3 辛基噻吩)(P3OT),利用核磁共振氢谱确定产物中含有摩尔分数为60%的头尾(HT)结构。通过改变良溶剂三氯甲烷与不良溶剂甲醇的体积配比,研究了P3OT的溶致变色行为,P3OT的紫外吸收峰随着甲醇用量的增加发生红移,在φ(CH3OH)=70%时,吸收峰从纯三氯甲烷溶液的435nm红移至490nm。在室温和0℃下,研究了紫外-可见吸收光谱随温度的变化,温度降低,P3OT的吸收峰发生蓝移。以400nm的光激发P3OT的三氯甲烷溶液,在573nm处得到了稳定的发射峰。     

Synthesis and Spectral Studies of 6,13-di (p-hydroxyphenyl) Pentacene and 6,13-di (p-hydroxynapthyl) Pentacene

Synthesis of 6,13-di (p-hydroxyphenyl) pentacene (PP-H) and 6,13-di (p-hydroxy napthyl) pentacene (PN-H) using 6, 13-pentacenequinone (PENTA) is reported. The PP-H and PN-H obtained were identified by ¹H NMR, and infrared spectra. Substitution with hydroxy phenyl group or hydroxy Napthyl group at the C-6 and C-13 positions of pentacene leads to phenomenal enhancement in solubility and photooxidative stability. XRD results showed that the pattern of PP-H and PN-H was different from the patterns of PENTA. UV-Visible spectra showed that the λmax of PP-H and PN-H in CHCl₃. The fluorescence spectra showed that PP-H (449 nm) and PN-H (396 nm) emitted purple when exited by UV radiation while only emitted red (PP-H 597 nm and PN-H 616 nm) when exited with visible light.     

Fluorescence of Cascade Blue™ inside nano-sized porous shells of silicate

Cascade Blue™ (CB) dye at a concentration as high as 0.227 M was encapsulated within nano-sized porous silicate shells, and its relative fluorescence yield determined over the pH range of 1.8–12.3, using 380 nm as the excitation wavelength. The results were compared with those obtained in aqueous solution using similar pH and total dye concentration. Near neutral pH, the relative fluorescence yields of CB inside the shells exhibited little fluorescence quenching, even though a high concentration of the dye was trapped inside the particles, while the peak wavelength of fluorescence was shifted from 420 nm in solution to 430 nm in shells. Both in shells and solution, the relative fluorescence intensity decreased as the solution pH was raised from 2 to 4, and in shells it nearly disappeared at about pH 3–4. As the pH was further increased, the red shift of fluorescence peak in the shell-trapped dyes was evident at pH 5 and its fluorescence intensity regained equal to that in acid. In the neutral pH range, the fluorescence intensity of CB in the shells was similar to that of the equivalent total concentration of the CB in solution. In solution, a similar red shift of the fluorescence maximum of CB to 430 nm was observed only above pH 9. These observations suggest that the fluorescence intensities of dyes trapped inside nano-sized porous silicate shells can be equal to or higher than that observed in solution under comparable conditions, leading to several hundreds times more fluorescent intensity when it is measured per single shell rather than per unit fluorophore.     

A novel azathia-crown ether dye chromogenic chemosensor for the selective detection of mercury(II) ion

A novel azathia-crown ether dye was synthesized and characterized and its binding ability with metal ions was investigated via UV–vis spectroscopy. When a series of alkali-metal, alkaline earth metal and transition metal ions were mixed with the dye in acetonitrile, only Hg²⁺ induced a large blue shift from 478 nm to 369 nm corresponding to a distinct color change from red to yellow, which made it possible to distinguish Hg²⁺ from other metal ions by the naked-eye. The excellent Hg²⁺-selectivity of the dye was attributed to the formation of a 1:2 dye:Hg²⁺ coordination complex which was demonstrated by means of a Job's plot.