吩噻嗪功能化的螺-9,9′-氧杂蒽芴的设计、合成及其光电性质与分子结构间的相互关系研究

合成了一种具有深的HOMO(-6.15 e V)分子轨道和高三线态能级(T_1,2.82 e V)的新型化合物10-(2-螺-9,9'-氧杂蒽芴基)吩噻嗪(SFXPz)。因其宽的能带结构(E_g,4.22 e V)和深的HOMO能级而有望制备高效蓝色有机电致磷光器件。热重分析和差热扫描曲线表明,该化合物具有良好的热稳定性(T_d,259℃)和高的形态稳定性(T_g,206℃)。完全相互分离的HOMO和LUMO轨道有利于阻止分子内能量反转。SFXPz的紫外吸收峰分别位于230,260,292和310 nm左右;其荧光光谱两个发射峰分别位于311,324 nm左右。此外,该化合物的分子结构经LC-MS、~1H NMR和~(13)C NMR进行了详细表征。     

不同电子取代基卟啉化合物的光谱和DFT研究

采用实验与密度泛函理论计算(DFT)相结合,研究了不同电子取代基修饰的5-邻羟基苯基-10,15,20-三苯基卟啉(TPPOH)和5-邻羟基苯基-10,15,20-三(对甲氧基)苯基卟啉[(p-OCH₃)TPPOH]化合物的吸收光谱及其电化学性质。结果表明,相对于TPPOH,由于对位甲氧基(-OCH₃)给电子能力强致使(p-OCH₃)TPPOH的卟啉环电子云密度增加,从而引起吸收光谱红移(3 nm)、氧化还原电位发生明显的负移,最高占据分子轨道(HOMO)和最低空轨道(LUMO)能级差降低0.06 eV。DFT理论分析分子前线轨道电子分布结果显示(p-OCH₃)TPPOH的HOMO和LUMO轨道能量均增加,而能级差却比TPPOH能级差小0.05 eV。理论结果与电化学和光谱实验结论一致,并进一步阐明了光谱和电化学性质变化机理,为揭示不同取代基卟啉化合物的设计与应用提供重要依据。     

2-巯基-5-硝基苯并咪唑振动光谱的密度泛函理论研究

选用密度泛函理论中的B3LYP杂化泛函,在B3LYP/6-31++g(d,p)（C,H,N,S）水平下,优化了2-巯基-5-硝基苯并咪唑分子（MNBMZ）的结构,优化结果表明,2-巯基-5-硝基苯并咪唑分子是一个近平面结构。通过频率计算,获得了2-巯基-5-硝基苯并咪唑分子（MNBMZ）的拉曼光谱,并和实验获得的拉曼光谱图进行了对比,200～800 cm-1波数段实验获得的拉曼谱带波数和理论计算波数相比,有一定程度的蓝移,800～1 800 cm-1波数段实验获得的拉曼谱带波数和理论计算波数相比,发生了一定的红移。对实验和理论计算光谱主要振动峰进行线性回归拟合,相关系数r=0.998,标准偏差14.98。实验和理论计算获得的拉曼光谱图基本上是一致的,表明本文选取的DFT理论计算方法是可靠的。结合VEDA4软件对2-巯基-5-硝基苯并咪唑分子的拉曼谱带简正振动模式进行了指认。此外,分析并讨论了2-巯基-5-硝基苯并咪唑分子（MNBMZ）前线轨道及HOMO,LUMO轨道的组成,HOMO和LUMO轨道能级差为3.31 eV,电子有从HOMO跃迁到LUMO的趋势。HOMO轨道中S原子的贡献是52.53%,LUMO轨道中硝基N和O原子的贡献分别为23.03%,19.97%和19.36%。采用含时密度泛函理论（time dependent density functional theory,TDDFT）对2-巯基-5-硝基苯并咪唑分子（MNBMZ）的激发态进行了计算分析,计算结果表明甲醇溶剂中2-巯基-5-硝基苯并咪唑分子（MNBMZ）理论计算的吸收波长为213,281和437 nm;实验获得的吸收波长223,272和353 nm。对研究2-巯基-5-硝基苯并咪唑分子的性质,提供了理论基础。     

一种苯磺酰基/螺-9,9′-氧杂蒽芴双极性分子的简易合成法:分子结构与光电性质

利用一种简易合成法制备了2′-苯磺酰基-螺-9,9′-氧杂蒽芴(PSSFX)。热重分析曲线和差热扫描曲线表明该化合物在222℃时失重5%,加热到160℃没有玻璃化转变温度,其熔点为124℃。通过磷光光谱计算得到该化合物的三线态能级T_1为2.77 eV。利用密度泛函计算得知其HOMO(-5.83 eV)和LUMO(-1.62 eV)轨道相分离。通过循环伏安法得到其HOMO、LUMO和E_g分别为-6.33,-2.34, 3.94 eV。这表明缺电子的苯磺酰基有利于改善其电子注入/传输性能。PSSFX在二氯甲烷溶液和晶体粉末的紫外吸收峰分别位于267 nm和274/351 nm左右,发射峰分别位于408 nm和341 nm左右。     

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。     

苯乙烯化苯酚的密度泛函研究

以苯乙烯化苯酚(SP-2)为研究对象,采用密度泛函理论的M06-2X/6-311g(d,p)方法,进行了分子结构优化.在此基础上,对其分子轨道、能级、最高占据轨道(HOMO)和最低空轨道(LUMO)、红外光谱(IR)、核磁共振谱(NMR)、紫外-可见吸收光谱(UV-Vis)进行了模拟计算.根据能级和分子轨道计算结果,主要讨论了苯乙烯化苯酚的最高占据轨道(HOMO)和最低空轨道(LUMO)的特点;获得了红外光谱(IR)、核磁共振谱(NMR)、紫外-可见吸收光谱(UV-Vis)计算结果,并对谱图数据进行了分析讨论.     

掺杂离子型配合物的高效聚合物白光发光二极管

研究了掺杂离子型铱配合物的单发光层聚合物白光器件.根据二元互补色获得白光的原理,所采用离子型橙光材料为六氟磷酸合[二(2-(萘基-1-基)吡啶)(1-乙基-2-(9-(2-乙基己基)-9H-咔唑-3-基)-1H-咪唑并[4,5-f][1,10]菲啰啉)铱(Ⅲ)]([(npy)₂Ir(c-phen)]PF₆),天蓝光材料为二(2-(4,6-二氟苯基)吡啶-N,C(2))吡啶甲酰合铱(Firpic).器件结构为氧化铟锡/苯磺酸掺杂聚乙烯基二氧噻吩(40 nm)/发光 关键词： 聚合物发光二极管 白光 二元互补色 离子型铱配合物     

过渡金属W、Mn、V、Ti掺杂二维材料MoSi2N4的第一性原理计算

本文基于密度泛函理论(DFT)的第一性原理计算了W、Mn、V、Ti替位掺杂二维MoSi₂N₄后的几何结构、电子结构以及光学性质的变化.电子结构分析表明W、Mn、W、Ti替位掺杂二维MoSi₂N₄后的禁带宽度分别为1.806 e V、1.003 e V、1.218 e V和1.373 e V;四种过渡金属掺杂后MoSi₂N₄的带隙类型没有发生改变,均为间接带隙半导体;W掺杂后的杂质能级靠近价带顶,费米能级靠近价带顶,为p型半导体,杂质能级为受主能级;Mn掺杂后的杂质能级靠近导带底,费米能级靠近导带底,为n型半导体;V和Ti掺杂后杂质能级位于费米能级附近,为复合中心;光学性质分析表明,在2 e V～4 e V的能量区间内,W掺杂结构的吸收波长为336 nm,体系发生红移;Mn、V和Ti替位掺杂后的吸收波长分别为320 nm、358 nm和338 nm,且掺杂体系均发生蓝移.     

羟基四苯咪唑衍生物的空穴和电子传输性质研究

随着有机发光二极管应用范围的扩大，对发光材料的研究逐渐增多。蓝光材料因其在色温管理和显色指数方面的重要作用，促使科学家们对效率更高、性能更好的新型蓝光材料进行了大量研究。通过（含时）密度泛函理论方法，对给电子取代基9,9-二甲基-9,10-二氢吖啶（DMAC）、三苯胺（TPA）、10H-吩噁嗪（PTZ）、10H-吩嗪（PXZ）、苯基咔唑（PCz）和5H-吲哚[3,2,1-de]吩嗪（InPz）双取代的羟基四苯咪唑分别进行了结构优化，并研究了其光物理性质。理论计算结果表明，TPA、DMAC、PTZ、PXZ和InPz取代的羟基四苯咪唑可作为空穴传输材料，PTZ、PXZ和InPz取代的羟基四苯咪唑可作为电子传输材料。     

新型氟代三苯胺衍生物的合成和光谱特性研究

设计和合成了一种新型氟代三苯胺衍生物——N,N,N′,N′-四苯基-[2′,2″,3′,3″,5′,5″,6′,6″-八氟对四联苯]-4,4″′-二胺(OFTPA)。通过元素分析、熔点测定、红外光谱和1 H NMR谱等手段对OFTPA的分子结构进行了表征,并对其主要的红外光谱吸收峰和1 H NMR谱带进行了归属分析。利用紫外-可见吸收光谱、荧光光谱和循环伏安法(CV)对OFTPA的电子能级结构和发光性能进行了研究。紫外-可见吸收光谱测定结果表明,OFTPA薄膜的最大吸收峰波长为355nm,光学带隙(Eg)为3.09eV。荧光光谱测定结果表明,OFTPA薄膜在365nm紫外光的激发下,产生发光峰波长在448nm附近、半峰宽(FWHM)为68nm的蓝光发射,色纯度高,有望成为优良的蓝光发射材料。循环伏安法测定结果表明,OFTPA的最高占有轨道(HOMO)能级为-5.41eV,最低空轨道(LUMO)能级为-2.32eV,具有良好的空穴传输性能。研究结果为进一步研究其在有机光电器件中的应用提供了参考。     

Spectroscopic Studies on Photoelectron Transfer from 2-(furan-2-yl)-1-phenyl-1H-phenanthro[9,10-d]imidazole to ZnO,Cu—doped ZnO and Ag—doped ZnO

The 2-(furan-2-yl)-1-phenyl-1H-phenanthro[9,10-d]imidazole [FPI] has been designed and synthesized as fluorescent sensor for nanoparticulate ZnO. The present work investigates the photoelectron transfer (PET) from FPI to ZnO, Cu-doped ZnO and Ag- doped ZnO nanoparticles using electronic and life time spectral measurements. Broad absorption along with red shift indicates the formation of charge-transfer complex [FPI?Nanoparticles]. The photophysical studies indicate lowering of HOMO and LUMO energy levels of FPI on adsorption on ZnO due to FPI? ZnO interaction. The obtained binding constant implies that the binding of FPI with nanoparticles was influenced by the surface modification of ZnO nanoparticles with Cu and Ag.     

Sensitive and Selective PET-Based π-expanded Phenanthrimidazole Luminophore for Zn2+ Ion

The novel photoinduced electron transfer (PET) chemosensor, 1-(1-(4-methoxyphenyl)-1H-phenanthro[9,10-d]imidazol-2-yl)naphthalen-2-ol [MPPN] and its zinc complex were synthesised and characterized by electronic spectral and Frontier molecular orbital energy analysis. MPPN becomes efficient fluorescent chemosensor upon binding with metal ions and shows a strong preference toward Zn²⁺ ion. Density Functional theory (DFT) calculations reveal that luminescence of free MPPN originates from its orbital structure in which two π-orbitals (HOMO and HOMO-1) of the imidazole ring are situated between two π-orbitals (HOMO-2 and LUMO) of the naphthyl fragment. Therefore the absorption and emission processes occur between the two π- orbitals (HOMO-2 and LUMO). The two higher energy imidazole orbitals (HOMO and HOMO-1 ) serve as quenchers for the excited state of the molecule through nonradiative processes. Upon binding with Zn²⁺ ion, MPPN becomes a highly luminescent with λ_emi???421 nm. The significant enhancement of luminescence upon binding with Zn²⁺ ion is attributed to the stabilization of HOMO-2 and HOMO-1 π-orbitals of imidazole ring upon their engagement in new bonds with Zn²⁺ ion. The affinity of MPPN to zinc ion is found to be very high [K?=?6?×?10⁶ M^?1] when compared with other metals ions. The nonlinear absorption coefficient γ for MPPN is 1.9?×?10^?12 m/W and 3.9?×?10^?11 m/W for MPPN-Zn complex.     

Structural,Electronic and Charge Transfer Studies of Highly Sensitive Fluorescent Probe 2-((E)-2-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)vinyl)phenol: Quantum Chemical Investigations

This article presents a facile synthesis of novel class of bluish-green fluorescent 2-((E)-2-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)vinyl)phenol [PPIVP] and their optical, electrochemical and thermal properties. Detailed photophysical and quantum chemical studies have been performed to elucidate the origin of the dual emission shifts. PPIVP undergo excited state intramolecular proton transfer (ESIPT) reaction leading a large Stoke’s shifted fluorescence emission from the phototautomer. The results of quantum chemical investigations not only confirmed the intramolecular charge transfer characteristics of the ESIPT tautomers but also provided a rational for the observed high fluorescence quantum efficiency in the solid state. The high photoluminescence quantum yield in the solid state is ascribed to twisted chromophores due to phenyl substituents at 1,2-position of the phenanthroimidazole ring which restricted intramolecular motion, leading to an optically allowed lowest optical transition without self quenching.     

Ab initio study for structure, electric properties and light emission of linear-trans-quinacridone

The structure, electric properties and emission rate of linear-trans-quinacridone are investigated within the density functional theory (DFT) calculations. We find the structure of the molecule to be planar with an energy gap of 3.06 eV. The emission lifetime from the lowest unoccupied molecular orbital (LUMO) to the highest occupied molecular orbital (HOMO) of this material is found to be 24 ns, which is in good agreement with experimental results.     

Density functional theory design D-D-A type small molecule with 1.03 eV narrow band gap: effect of electron donor unit for organic photovoltaic solar cell

Six new low-band-gap copolymers of donor–donor–acceptor (D-D-A) architecture have been designed using density functional theory and time-dependent density functional theory methods in order to use them in organic photovoltaic cell (OPVC). Phenanthro[3,4-d:9,10-d′]bis([1,2,3]thiadiazole)-10,12-dicarbonitrile moiety has been used as an acceptor for all compounds. We insert benzo[1,2-b:4,5-b′]dithiophene and N,N-diphenylbenzo[1,2-b:4,5-b′]dithiophen-2-amine units as donor to complete designing of copolymers. In order to tuning the optical and electronic properties, we have modified the donor unit by substituted with amine, methoxyamine, N-methylenethiophen-2-amine, methoxy, alkoxy moieties. The band gap (E_g), HOMO and LUMO values and plots, open circuit voltage (V_OC) as well as optical properties have been analysed for designed copolymers. The optimised copolymers exhibit low-band-gap lying in the range of 1.03–2.24 eV. DPTD-6 copolymer presents the optimal properties to be used as an active layer due to its low E_g (1.03 eV) and a moderate V_OC (0.56 eV). Thus, OPVC based on this copolymer in bulk-heterojunction composites with [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as an acceptor has been modelled. E_g and V_OC values of composite material DPTD-6:PCBM are found as 1.32 and 0.65 eV, respectively. A model band diagram has been established for OPVC, simulating the energy transfer between active layers.     

苯基酞嗪类三环铱配合物的合成及其电致发光性能

通过含苯氧基团的苯基酞嗪衍生物配体与IrCl₃一步反应生成了三环铱配合物Ir(mppppz)₃。在480 nm光激发下其二氯甲烷溶液的发光波长为608 nm,量子产率约为0.31,磷光寿命为268 ns,其纯固态发光波长为640 nm。配合物的HOMO能级为5.14 eV,LUMO能级为2.91 eV。当Ir(mppppz)₃以2%的质量分数掺杂于PVK-PBD中做成电致发光器件后,电致发光波长为616 nm。器件的启亮电压为3.9 V,最大外量子效率为1.48%,最大亮度为1 030 cd/m²,对应的流明效率为0.81 cd/A,所发出的光的色坐标是(0.64, 0.35),接近标准红色。     

Covalent functionalization of AlN nanotubes with acetylene

Covalent functionalization of a zigzag AlN nanotube (AlNNT) with acetylene molecule has been investigated using density functional theory in terms of energetic, geometry and electronic properties. The obtained results show that the acetylene preferably tends to [2+2] addition on Al–N bonds of the tube surface releasing energies in the range of 1.02 to 1.10 eV along with a charge transfer from the tube to the acetylene. We have found that HOMO–LUMO gap of AlNNT has not changed significantly upon the functionalization and, its global hardness and electrophilicity are slightly decreased. Also, it has been revealed that the field electron emission from the AlNNT surface may be improved upon the adsorption of acetylene due to decrease of work function ascribed to the charge transfer from the tube to the acetylene.     

A density functional theory investigation of the stability,aromaticity, and photophysical behavior for the highly conjugated macrocycles containing 4 pyrroles

Porphyrin ( Pr ), porphycene ( Pc ), and [22]porphyrin(2.2.2.2) ( P[22] ) have been theoretically investigated. We design 2 highly conjugated macrocycles containing 4 pyrroles with different linkage bridges, which are named for 4 pyrrole ( Pf ) and methylene‐dipyrrolidine ( Pm ), as the theoretical model so as to investigate the stability, aromaticity, and photophysical behavior of these porphyrin derivatives, and the influence of getting or losing electron to the neutral molecule. The geometric structures of the molecules are optimized by density functional theory method. The absorptions are calculated by the time‐dependent density functional theory method. Based on the optimized structures, the nucleus‐independent chemical shifts (NICS) are calculated. The molecule with negative NICS value possesses larger highest occupied molecular orbital (HOMO)‐lowest occupied molecular orbital (LUMO) gap than that with positive NICS value, the molecule with bigger positive NICS value possesses smaller HOMO‐LUMO gap, and the molecule with bigger negative NICS value (in absolute value) possesses bigger HOMO‐LUMO gap. The current density indicates that the π‐electron delocalization is more effective in Pr and Pc than in Pf , Pm , and P[22] and corresponds to the stability of molecules. The absorptions of the molecules are all in the UV‐visible and infrared regions. The major transitions for most of the molecules are all from HOMO to LUMO. Compared with Pf ^2? , Pr ^2? , Pc ^2? , and P[22] ^2? , Pm ^2? shows distinctive photophysical properties, which is due to the reduced HOMO‐LUMO gap, structural distortion, and strong antiaromaticity.     

以双(2-二苯基磷苯基)醚为配体的蓝色磷光铜(Ⅰ) 配合物的合成及光电特性研究

合成了一种新型的室温天蓝色磷光发射材料双(2-二苯基磷苯基)醚碘合铜(Ⅰ)([(POP)CuI]₂)配合物。通过红外光谱、X-射线单晶衍射确定其分子结构,并对其光电特性进行了详细研究。结果表明:[(POP)CuI]₂为二聚体结构,主要吸收峰为227,268,291 nm,最大发射峰为475 nm,光学带隙为2.93 eV。以[(POP)CuI]₂作为客体掺杂在主体CBP中作为发光层,制备了结构为ITO/NPB(30 nm)/CBP∶[(POP)CuⅠ]₂(30 nm,8%)/BAlq(10 nm)/Alq₃ (30 nm)/LiF(1 nm)/Al(200 nm)的器件,其电致发光峰为476 nm,最大亮度为9 539 cd/m²,最大电流效率为1.9 cd/A。     

Synthesis, Fluorescence Properties and Theoretical Calculations of Novel Stilbene Derivatives Based on 1,3,4-Oxadiazole Bearing Anthracene Core

Two novel stilbene derivatives bearing anthracene core based on 1,3,4-oxadiazole were efficiently synthesized and characterized by ¹H-NMR, mass spectrometry and elemental analysis. The optical properties of the title compounds were investigated by UV–vis absorption and fluorescence emission spectra in different solvents. Chemical calculations were performed by density functional theory (DFT) at the (B3LYP)/6-31G* level. The results show the two compounds exhibit strong green fluorescence emission ranged from 489–493 nm, and the fluorescence quantum yield ranged from 0.78–0.92. Their HOMO and LUMO levels are (?5.44 eV, ?2.25 eV) and (?5.45 eV, ?2.28 eV), respectively. The influence of the solvent on the fluorescence intensities was also discussed.