新型双光子聚合引发剂的合成和非线性光学性质的研究

合成了两种新的双光子聚合引发剂反式-二苯基-{{4-[2-(4-吡咯基-1-苯基)-乙烯基]-苯基}胺(简称DPVPA)和反式-9-{4-[2-(4-吡咯基-1-苯基)-乙烯基]-苯基]-9-氢咔唑(简称PPVPA).用1H NMR谱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、单光子荧光寿命和双光子荧光光谱.在760 nm的飞秒脉冲激光激发下,DPVPA和PPVPA均发出较强的上转换荧光,荧光峰分别位于468和452 nm.以DPVPA做引发剂,加入丙烯酸酯型齐聚物(CN120C80),用DATACHROOM-5000纳秒激光器辐射出600nm的激光做光源,实现了双光子聚合反应,并定性地解释了其聚合机理.     

含二乙氨基苯基三取代结构双光子聚合引发剂的合成

合成了一种新型三取代结构的双光子聚合引发剂1,3,5-三[4-(N,N-二乙氨基)苯基]乙烯基]苯基]苯(4),通过元素分析、电喷雾质谱、1 H NMR和红外谱对其进行表征。测试了紫外吸收光谱、单光子荧光光谱和双光子荧光光谱,并测出其双光子吸收截面为9.87×10-48cm4.s/photon。利用合成的1,3,5-三[4-(N,N-二乙氨基)苯基]乙烯基]苯基]苯作双光子聚合引发剂,以甲基丙烯酸甲酯齐聚物作单体(CN120C80),200fs,76MHz、Ti:sapphire飞秒激光器作光源,进行了三维周期微结构的制作。所合成化合物是潜在应用前景的双光子吸收材料。     

[1,3,4]-噁二唑衍生物的固相合成及其线性、非线性光谱性质

用固相法合成了2个噁二唑衍生物类有机化合物:5-(4-叔丁基苯基)-[1,3,4]噁二唑-2-苯乙烯基-4-苯基-二苯胺 (化合物1)与9-乙基-3,6-双{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基}-咔唑 (化合物2),并测定了它们的吸收光谱、单光子荧光光谱和双光子荧光光谱.化合物1和2在二氯甲烷溶液中单光子荧光发射峰分别位于519和476nm.在锁模Nd∶YAG激光器800nm激光照射下,化合物1和2发射出很强的双光子上转换荧光,其最大波长分别在520和485nm.     

一种三取代结构双光子吸收材料的合成

合成了一种新型三取代结构的双光子吸收材料1,3,5-三[4-[2-(3-吡啶)乙烯基]苯基]苯(4),通过元素分析、电喷雾质谱、1HNMR和红外对其进行表征。测试了紫外吸收光谱、单光子荧光光谱和双光子荧光光谱,并测出其双光子吸收截面为7.63×10-48cm4.s.photon-1。利用合成的1,3,5-三[4-[2-(3-吡啶)乙烯基]苯基]苯作引发剂,以甲基丙烯酸甲酯齐聚物作单体(CN120C80),200fs,76MHz、Ti∶sapphire飞秒激光器作光源,进行了三维周期微结构的制作。所合成化合物是潜在应用前景的双光子吸收材料。     

含噻吩基三取代双光子吸收材料的合成

合成了一种新型三取代结构的双光子吸收材料1,3,5-三[4-[2-(噻吩)乙烯基]苯基]苯,通过元素分析、1 H NMR和红外光谱对其进行表征。测试了材料的紫外吸收光谱、单光子荧光光谱和双光子荧光光谱,并测出其双光子吸收截面为426×10-50cm4·s·photon-1。以1,3,5-三[4-[2-(噻吩)乙烯基]苯基]苯为引发剂,甲基丙烯酸甲酯齐聚物(CN120C80)为单体,飞秒激光器(200fs、76 MHz、Ti∶sapphire)为发光源,进行了三维周期微结构的制作。     

一种新型含卟啉的环金属化有机配体的设计、合成与性质

采用Aldol、Adler缩合、Michael加成、Vils-meier和Knoevenagel等反应合成一种新型的D-π-A型的含C∧N∧N结构的环金属化有机配体：反式-4-[2-（5,10,15,20-四苯基卟啉基）乙烯基]-N-{4-[（2-苯基-6-吡啶基）吡啶]苯甲基}吡啶溴盐（简写为TPPB）。用核磁共振氢谱、碳谱和电喷雾质谱等手段对其结构进行了表征,初步研究了该化合物的紫外-可见光谱、荧光光谱、电化学和热稳定性。结果表明目标化合物有较好的溶解性和荧光性质,为寻找新的发光材料进行了有益的探索。     

三苯胺多枝化合物的合成及其荧光性质

采用Heck反应合成了2个三苯胺多枝化合物N,N,N-三{5-(4-叔丁基苯基)-1,3,4-噁二唑-2-苯乙烯基-4-苯基}胺(化合物1)和N,N,N-三[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}胺(化合物2),并测定了它们的吸收光谱、单光子荧光光谱和双光子荧光光谱.化合物1和2在二氯甲烷溶液中单光子荧光发射峰分别位在536和487nm.在锁模Nd:YAG激光器800nm激光照射下,化合物1和2发射出很强的双光子上转换荧光,其最大波长分别在541和518nm.     

聚乙二醇双丙烯酸酯的紫外光聚合

以1-[4-(2-羟乙氧基)-苯基]-2-羟基-2甲基丙酮为光引发剂,通过紫外光自由基聚合制备了交联网状聚乙二醇双丙烯酸酯共聚物水凝胶。研究结果表明,随着光照时间的增加,单体共聚的转化率提高;随着引发剂浓度的增大,单体溶液中自由基增多,聚合速度增大。FI-IR结果表明PEGDA单体经30min紫外光照射后聚合完全。     

一种共轭有机杂环分子的双光子吸收与电化学性质

实验研究了一种新的共轭杂环化合物9-乙基-3-{5-(4-叔丁基苯基)-[1,3,4]-噁二唑-2-苯乙烯基}-咔唑(VBPOEC)的双光子吸收性质和电化学性质.双光子吸收截面采用非线性透过率法测定,双光子最大吸收波长位于800nm,吸收截面为1350GM.采用紫外光谱的边带吸收法得到带隙为2.77eV,用循环伏安法对其电化学性质进行了初步研究,氧化电位为1.059V,其HOMO能级为-5.80eV,其LUMO轨道能级为-3.03eV.研究了光学、电化学性质与分子电子结构的关系.     

通过具有高表面能和延长共轭链段的耐溶剂空穴传输材料实现高效喷墨打印QLED（英文）

量子点发光二极管(QLED)溶液法制备的特点和喷墨打印高度契合,在印刷显示器领域展现出巨大的应用潜力.制作QLED器件时,下层薄膜的表面能对上层薄膜的铺展起着至关重要的作用,高表面能可以促进不同功能膜层之间的紧密接触并减少漏电流.然而,已报道的交联空穴传输材料(HTM)低的表面能不利于喷墨打印.在此,我们通过分子设计开发了一种可交联HTM及其聚合物,新的聚合物命名为[9-(4-(乙氧基甲基)苯基)-3-(7-(9-(4-(己炔基)乙氧基甲基)苯基)-9H-咔唑-3-基)-9H-芴]-9H-咔唑(PDA-FLCZ),由3,3′-(9,9-二甲基-9H-芴-2,7-二基)双[9-(4-(丙-2-炔-1-氧基)甲基)苯基]-9H-咔唑(DA-FLCZ)聚合得到.这种新型HTM采用原位光热交联和预聚后热交联两种交联策略,都可以在较低的交联温度下形成稳定的网络结构,具有优异的耐溶剂性和较高的表面能.通过优化交联工艺,交联PDA-FLCZ薄膜实现了更高的空穴迁移率和更低的陷阱密度,其对应的旋涂QLED器件的最大外量子效率(EQE)达到17.59%,比基于DA-FLCZ的器件(14.25%)高出23...     

Two new asymmetrical two-photon photopolymerization initiators: Synthesis, characterization and nonlinear optical properties

Two new asymmetrically free-radical two-photon photopolymerization initiators, Diphenyl-{4-[2-(4-pyrrolidin-1-yl-phenyl)-vinyl]-phenyl}-amine (abbreviates to DYVPA) and 9-{4-[2-(4-Pyrrolidin-1-yl-phenyl)-vinyl]-phenyl}-9H-carbazole (abbreviates to PPVPA), have been synthesized and characterized. Linear absorption, one-photon fluorescence emission and their lifetimes, and two-photon fluorescence emission have been investigated. The calculated two-photon absorption cross-sections of DYVPA and PPVPA are 70.1 and 28.0 × 10⁻⁵⁰ cm⁴ s photon⁻¹, respectively. Microfabrications via two-photon initiating polymerization have been studied and the possible photopolymerization mechanism is discussed.     

Synthesis and nonlinear optical properties of two new two-photon initiators: Triphenylamine derivatives

Two new two-photon polymerization initiators, 1-{(1E)-2-[4-(diphenylamino)phenyl]vinyl}-4-[4-N,N-di-methylamino]benzene (PVMB) and 1-[(1E)-2-(4-{[4-((1E)-2-{4-[4-N,N-di-methylamino]phenyl}vinyl)phenyl]phenylamino}phenyl)vinyl]-4-[4-N,N-di-methylamino]benzene (DPVMB) have been synthesized with solid phase Wittig reaction. The single-photon fluorescence, quantum yields, lifetimes, solvent effects of the initiators were studied in detail and both compounds exhibited solvent-sensitivity. Two compounds are good two-photon absorbing chromophores and operative two-photon photopolymerization initiators. Two-photon absorption (TPA) cross-sections from 730 nm to 870 nm at intervals of 10 nm have been measured with the two-photon-induced fluorescence method, and the maximal values of the TPA cross-sections of PVMB and DPVMB are 1.6 GM and 19.9 GM (1 GM = 1 × 10⁻⁵⁰ cm⁴ s photon⁻¹ molecule⁻¹) at 800 nm, respectively. A microstructure has been fabricated by using DPVMB as initiator.     

Thermally and electrochemically stable amorphous hole-transporting materials based on carbazole dendrimers for electroluminescent devices

Amorphous hole-transporting carbazole dendrimers, 1,4-bis[3,6-di(carbazol-9-yl)carbazol-9-yl]-2,6-di(2-ethylhexyloxy)benzene (G2CB) and 1,4-bis[3,6-di(carbazol-9-yl)carbazol-9-yl]-9-(2-ethylhexyl)carbazole (G2CC), were synthesized by a divergent approach involving bromination and Ullmann coupling reactions. Compounds G2CB and G2CC showed high thermal stability (T_g = 206 to 245 °C) and excellent electrochemical reversibility. Double-layer organic light-emitting diodes were fabricated by using G2CB and G2CC as hole-transporting layers (HTLs) and tris(8-quinolinato)aluminum (Alq₃) as light-emissive layer with the device configuration of indium tin oxide/HTL/Alq₃/LiF:Al. Both devices exhibited bright green emission from Alq₃. The device using G2CC as HTL has the best performance with a maximum brightness of 8900 cd/m² at 14 V and a low turn-on voltage of 3.5 V.     

Synthesis and nonlinear optical properties of two new two-photon initiators: Triphenylamine derivatives

Two new two-photon polymerization initiators, 1-{(1E)-2-[4-(diphenylamino)phenyl]vinyl}-4-[4-N,N-di-methylamino]benzene (PVMB) and 1-[(1E)-2-(4-{[4-((1E)-2-{4-[4-N,N-di-methylamino]phenyl}vinyl)phenyl]phenylamino}phenyl)vinyl]-4-[4-N,N-di-methylamino]benzene (DPVMB) have been synthesized with solid phase Wittig reaction. The single-photon fluorescence, quantum yields, lifetimes, solvent effects of the initiators were studied in detail and both compounds exhibited solvent-sensitivity. Two compounds are good two-photon absorbing chromophores and operative two-photon photopolymerization initiators. Two-photon absorption (TPA) cross-sections from 730 nm to 870 nm at intervals of 10 nm have been measured with the two-photon-induced fluorescence method, and the maximal values of the TPA cross-sections of PVMB and DPVMB are 1.6 GM and 19.9 GM (1 GM = 1 × 10⁻⁵⁰ cm⁴ s photon⁻¹ molecule⁻¹) at 800 nm, respectively. A microstructure has been fabricated by using DPVMB as initiator.     

Efficient phosphorescent green and red organic light-emitting diodes based on the novel carbazole-type host material

We developed a novel carbazole-type material, 9-phenyl-3,6-bis(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-9H-carbazole (LPGH 153), and fabricated the green and red phosphorescent organic light-emitting diodes (OLEDs) using LPGH 153 as host. The red and green devices have the max. luminous efficiencies of 22.2 cd/A and 32.2 cd/A, respectively.     

双光子聚合引发剂DBASDMB的结构与光学性能的研究

制备了一种双光子聚合引发剂,反,反-1,4-双（4＇-N,N-二丁胺基苯乙烯）-2,5-二甲氧基苯（DBASDMB）,利用挥发溶剂法首次获得该化合物的晶体,用四圆X射线衍射法解析了晶体结构.结果表明,该晶体属于三斜晶系,P-1空间群;同时证明引发剂分子是具有很好对称性和平面性的全反式结构.仔细研究了该化合物在不同溶剂下的线性吸收光谱和单、双光子荧光谱,并在同一条件下对其单、双光子光谱进行了比较.在760nm的飞秒脉冲激光辐照下,DBASDMB能够高效地引发聚氨酯类丙烯酸酯齐聚物的聚合反应,成功地制作了一个微结构.     

Synthesis and photovoltaic properties of new near infrared absorption polymers based on C and N-bridged dithiophene and diketopyrrolopyrrole units

Two novel diketopyrrolopyrrole-based conjugated copolymers, namely, poly{[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl]-alt-[3,6-bis(bithiophen-5-yl)-2,5-di-(2-ethylhexyl)-pyrrolo[3,4-c]pyrrole-1,4-dione]} (P1) and poly{[N-(2-ethylhexyl)-dithieno[3,2-b:2′,3′-d]pyrrole-2,6-diyl]-alt-[3,6-bis(bithiophen-5-yl)-2,5-di-(2-ethylhexyl)-pyrrolo[3,4-c]pyrrole-1,4-dione]} (P2), have been designed and synthesized by Stille coupling reaction. The resulting copolymers exhibited very broad and strong absorptions in the visible and near-infrared region. Through cyclic voltammetry measurements, it was found that P1 possesses a lower highest occupied molecular orbital energy level (?5.14 eV) compared to that of P2 (?4.98 eV). The bulk heterojunction photovoltaic devices were fabricated by using the two copolymers as the donor and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as the acceptor in the active layer. The maximum power conversion efficiency of 1.48 % was obtained based on the blend of P1:PCBM = 1:3(w/w) with open circuit voltage (V _OC ) of 0.66 V and short circuit current (J _SC ) of 6.36 mA/cm², under the illumination of AM 1.5, 100 mW/cm².     

Blue organic light-emitting diodes based on solution-processed fluorene derivative

We report blue fluorescent organic light-emitting devices (OLED) by solution process utilizing a blue emitting small molecule, 2,7-bis[(9-ethyl-9H-carbazol-3-yl)ethenyl]-9,9-bis(4-n-octyloxyphenyl)-9H-fluorene (CB), which has good solubility in common organic solvent. The peak positions of absorption and emission spectra of a new fluorene-based molecule in tetrahydrofuran solution were observed at 399 and 439 nm, respectively. We achieved a maximum luminous efficiency of approximately 3 cd/A with CIE color coordinates of (0.15, 0.15) in our device.     

Excited-state absorption and anisotropy properties of two-photon absorbing fluorene derivatives

The electronic structure of fluorene derivatives N-(7-benzothiazol-2-yl-9,9-bis-decyl-9H-fluoren-2-yl)-acetamide (1); 9,9-didecyl-2,7-bis-(N,N-benzothiazoyl)fluorene (2); 4,4'-{[9,9-bis(ethyl)-9H-fluorene-2,7-diyl]di-2,1-ethenediyl}bis(N,N-diphenyl)benzeneamine (3); and 4,4',4"{[9,9-bis(ethyl)-9H-fluorene-2,4,7-triyl]tri-2,1-ethenediyl}tris(N,N-diphenyl)benzeneamine (4) were investigated by a steady-state spectral technique, quantum-chemical calculations, and a picosecond pump-probe method. These derivatives are of interest for their relatively high two-photon absorption. The steady-state excitation anisotropy spectra reveal the nature of the ground-state absorption bands. Semiempirical quantum-chemical calculations of the fluorene derivatives (AM1, ZINDO/S) show good agreement with experimental data. The spectral positions and alignment of various electronic transitions of derivatives 1-4 were estimated from their excited-state absorption and anisotropy spectra.     

Ion-induced manipulation of photochemical pathways in crown ether compounds based on fluorinated oligophenylenevinylenes: the border between ultrafast photoswitches and photoproduced nanomaterials

The photochemical and photophysical properties of the crown ethers trans,trans-1,4-bis[2-(3',4'-benzo 15-crown 5)ethenyl]-2,3,5,6-tetrafluorobenzene (1) and trans,trans-1,4-bis[2-(3',4'-benzo 18-crown 6) ethenyl]-2,3,5,6-tetrafluorobenzene (2) were investigated in the absence and presence of groups I and II metal ions. The photophysical methods used include steady state flurescence, uv spectroscopy, and ultrafast transient absorption spectroscopy. Both compounds showed solvatochromic behavior, due to intramolecular charge transfer state formation, and efficient fluorescence in polar solvents. Photophysical behavior was dependent on the metal ion. The addition of metal ions that completely fit into the crown ether cavity resulted in significant blue shifts in the fluorescence emission spectra (chemosensing properties). Partially fitting ions changed the fluorescence spectra slightly. Transient absorption measurements revealed fast and slow decay components with time constants of 10-20 and 500-600 ps for all fitting ions, respectively. The latter is assigned to a trans-cis photoisomerization process, which decreased in efficiency in the presence of partially fitting ions, i.e., increasing ion size. Steady state irradiation showed clear evidence of a change in the absorption spectra. Trans-cis photoisomerization and [2 + 2] photocycloaddition were found to compete with fluorescence. The ions Li+, Na+, and Ca2+, which fit into the cavity, direct the photoisomerization. Larger ions (K+, Rb+, Sr2+ and Ba2+) that partially fit the cavity cause photocycloaddition. Quantum yields of the photoreaction are between 0.1 and 0.3. Analysis of the photo-product obtained for the 1-Sr2+ system revealed a compound with a molecular weight of nanosize dimension, which was equivalent to seven mass units of 1. The higher molecular weight product was formed due to alternately stacked supramolecular assemblies.