新型蓝色有机电致磷光配合物二(2-二氟苯基-4-甲基吡啶)[2-(2′-吡啶基)咪唑]合铱的合成及光谱学性能

合成了三个以含氟苯基吡啶及吡啶基咪唑为配体的蓝色磷光电致发光铱配合物(P)2Ir(pym),其中主配体(P)分别为2-(2′,4′-二氟苯基)-4-甲基吡啶、2-(3′,4′-二氟苯基)-4-甲基吡啶、2-(3′,5′-二氟苯基)-4-甲基吡啶;辅助配体pymH为2-(2′-吡啶基)咪唑。通过元素分析、核磁、质谱、红外进行结构表征;用紫外可见吸收光谱、荧光光谱以及循环伏安进行其光谱学性能表征。以pymH取代辅助配体picH(2-吡啶甲酸)的方法,得到含吡啶基咪唑的铱配合物,在室温下二氯甲烷溶液中获得强的蓝光发射,其最大发光波长分别是461,480,490nm,其中(46fpmpy)Ir(pym)较经典蓝光磷光材料FIrpic蓝移5nm。     

新型苯乙烯衍生物掺杂的蓝色及白色有机电致发光器件

研究了新型高效蓝色掺杂剂EBDP的电致发光性能. 分别以EBDP为掺杂剂制备了结构为氧化铟 锡(ITO)/酞菁铜(CuPc)/N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺(NPB)/2- 叔丁基-9,10-二-(2-萘基)蒽(TBADN):EBDP/8-羟基喹啉铝(Alq₃)/LiF/Al 与ITO /CuPc/NPB/TBADN:EBDP: 4-二氰亚甲基-2-叔丁基-6-(1,1,7,7-四甲基久咯呢定基-9-烯基)- 4H-吡喃/Alq_{3 关键词： 有机电致发光 蓝色掺杂剂 蓝色电致发光器件 白色电致发光器件}     

N-(4-羟基-苯基)-甘草次酸酰胺的合成

以18β-甘草次酸和4-氨基苯酚为原料,在N,N＇-二环己基碳二酰亚胺(DCC),1-羟基苯并三唑(HOBt)/4-N,N-甲基吡啶(DMAP),N-甲基吗啉(NMM)作用下合成了N-(4-羟基-苯基)-甘草次酸酰胺,通过DCC、DCC/HOBt催化有机酸形成酯、酰胺反应的历程解释了在DCC/HOBt催化体系中目标化合...     

2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶及镍(Ⅱ)配合物的合成与光谱学研究

合成并表征了有机配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶(L)及其镍(Ⅱ)配合物,采用元素分析确定目标配合物组成为C15H21N3O4Ni.H2O,通过对比分析的方法讨论了配位前后游离配体L和镍(Ⅱ)配合物的核磁共振氢谱、核磁共振碳谱、红外吸收光谱和紫外-可见吸收光谱的谱学性质,进而推断出镍(Ⅱ)配合物的结构。结果表明,配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶以2个酰胺负离子N和1个吡啶环N原子为配位原子,与中心金属离子Ni(Ⅱ)通过三齿形式配位;配合物中Ni(Ⅱ)采取dsp2杂化轨道方式与配位原子构成配位键,中心金属Ni(Ⅱ)的配位数为4,1个Ni(Ⅱ)与1个三齿配体L和1个水分子配位,形成平面正方形构型的低自旋镍(Ⅱ)配合物。     

有机电光晶体4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐的太赫兹光谱研究

采用色散校正的密度泛函理论(dispersion-corrected density functional theory,DFT-D2)对有机电光晶体4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐(4-N,N-dimethylamino-4′-N′-methyl-stilbazolium tosylate,DAST)进行结构优化和太赫兹光谱计算,通过逐步提高精度进行几何优化的方法寻找DAST收敛的基态稳定结构,获得与DAST初始结构相一致的基态稳定结构.在此结构的基础上,在0—4 THz范围的太赫兹计算光谱与实验测量结果一致,说明采用DFT-D2进行优化的合理性.重要的是,首次通过计算的太赫兹光谱对DAST在0—4 THz范围的太赫兹吸收峰的振动模式进行了详细归属.结果表明:1.12 THz处的振动是DAST阴阳离子的光学声子模式,1.46 THz和1.54 THz两处的振动主要与磺酸盐有关,而2.63 THz和3.16 THz两处的振动则分别源于阳离子的扭转振动和阴离子的转动.该结果不仅很好地说明了阴阳离子分别在太赫兹响应中的贡献,而且为今后通过取代阴阳离子基团获取具有更高二阶非线性效应的DAST衍生物的新合成提供了重要的参考和指导.本文结果说明密度泛函理论在太赫兹光子学上的重要应用,对探究有机电光晶体的太赫兹响应物理原理、性能控制等具有重要的指导价值.     

新型蓝色有机电致磷光配合物二(2-二氟苯基-4-甲基吡啶) 合铱的合成及光谱学性能

合成了三个以含氟苯基吡啶及吡啶基咪唑为配体的蓝色磷光电致发光铱配合物(P)₂Ir(pym),其中主配体(P)分别为2-(2',4'-二氟苯基)-4-甲基吡啶、2-(3',4'-二氟苯基)-4-甲基吡啶、2-(3',5'-二氟苯基)-4-甲基吡啶;辅助配体pymH为2-(2'-吡啶基)咪唑。通过元素分析、核磁、质谱、红外进行结构表征;用紫外可见吸收光谱、荧光光谱以及循环伏安进行其光谱学性能表征。以pymH取代辅助配体picH(2-吡啶甲酸)的方法,得到含吡啶基咪唑的铱配合物,在室温下二氯甲烷溶液中获得强的蓝光发射,其最大发光波长分别是461,480,490 nm,其中(46f₂pmpy)₂Ir(pym)较经典蓝光磷光材料FIrpic蓝移5 nm。     

非线性光学晶体4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐的制备与性能研究

采用籽晶法制备了大体积高质量的4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐(DAST)晶体，对制备条件进行了优化，对DAST晶体X射线衍射谱图中的主要峰进行了指标化.另外，还对所制备的DAST晶体的透光性、热稳定性进行了研究， 并对265℃的焙烧产物进行了X射线衍射 (XRD)和傅里叶变换红外光谱(FT-IR)测试，证明了260℃是DAST晶体的熔化相变温度， 说明采用熔融法制备DAST晶体是可行的；同时还对DAST晶体的热失重过程进行了初步探讨. 关键词： 4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐 晶体生长 X射线衍射 热稳定性     

2-三氟甲基吡啶的转动光谱及分子结构研究（英文）

本文测定了2-三氟甲基吡啶在2～20 GHz频率范围内的高分辨转动光谱.测定了转动常数、~(14)N核四极耦合常数及离心畸变常数等一系列光谱参数.同时还在自然丰度下测定了5个~(13)C和1个~(14)N单取代同位素异数体的光谱数据.实验结果结合从头算准确地推导出2-三氟甲基吡啶的骨架结构.实验测得同位素异数体的平面转动惯量P_(cc)数值均为44.46 uA~2,表明此分子具有C_s对称性.此外,本文计算了吡啶、2-氟吡啶、2-甲基吡啶和2-三氟甲基吡啶的分子表面静电势,以此分析了三氟甲基的取代对电子分布的影响.     

光谱法研究Ni[(C4H9O)2PS2]2与氮碱的加合反应

用光谱法研究了Ni[(C4H9O)2PS2]2(NiL2)与吡啶、4-甲基吡啶、3,5-二甲基吡啶、2,4-二甲基吡啶和2,4,6-三甲基吡啶,温度为32℃时在乙醇溶剂中的加合反应.B(2,4-二甲基吡啶和2,4,6-三甲基吡啶)只能与NiL2生成一种1∶2的六配位加合物NiL2·B2,其他氮碱与NiL2生成1∶1的五配位NiL2·B和1∶2的六配位NiL2·B2两种加合物.所有五配位NiL2·B和六配位NiL2·B2加合物的吸收光谱分别由NiNS4和NiN2S4发色基团所产生.实验测定了加合反应的平衡常数lgβn和加合反应分子数n,lgβn随氮碱分子碱度pka增加而增大,且可以用经验公式来描述     

一种新型有机染料HEASPS在不同波长时的双光子吸收和频率上转换性质研究

报道了一种新型双光子吸收染料 ,即反式 - 4- [4′- (N-羟乙基 - N-乙基胺基 )苯乙烯基 ]- N-甲基吡啶对甲苯磺酸盐的非线性光学性质 ;测试了染料在 72 0～ 110 0 nm波段的非线性透过率曲线。结果发现 :双光子吸收最强波长相对线性吸收峰波长的两倍处有明显蓝移 ;计算出的相应波长的双光子吸收截面在 930 nm处染料有最大双光子吸收截面(2 .0 6× 10 - 4 7cm4·s/ photon) ;测量了染料在 90 0～ 110 0 nm波段的上转换效率 ,在 10 2 0 nm处有最高效率 (5 .1% ) ,最高激射效率的波长相对最强双光子吸收的波长有明显红移     

High-sensitive terahertz detection by parametric up-conversion using nanosecond pulsed laser

A high-sensitive terahertz detector operating at room temperature was demonstrated based on parametric upconversion.A nanosecond 1064-nm Nd:YAG laser was used to pump the parametric up-conversion detector and the upconversion from terahertz wave to NIR laser was realized in a lithium niobate crystal.The minimum detectable terahertz energy of 9 p J was realized with the detection dynamic range of 54 d B,which was three orders of magnitude higher than that of commercial Golay cell.The detectable terahertz frequency range of the detection system was 0.90 Thz–1.83 THz.Besides,the effects of pump energy and effective gain length on the detection sensitivity were studied in experiment.The results showed that higher pump energy and longer effective gain length are helpful for improving the detection sensitivity of parametric up-conversion detector.     

Widely tunable broadband terahertz radiation generation using a configurationally locked polyene 2-[3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene] malononitrile crystal via difference frequency generation

Widely tunable terahertz (THz) waves were successfully generated from 0.5 to 10 THz via difference frequency generation (DFG) in a configurationally locked polyene 2-[3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene] malononitrile (OH1) crystal. Potassium titanium oxide phosphate optical parametric oscillator pumped by nanosecond Q-switched Nd:YAG laser was used to generate two waves, which were then used to irradiate OH1 crystal. The maximum energy of the generated THz wave was about 461 pJ/pulse. We investigated the dependency of generated THz energy to the excitation pump power density and OH1 crystal thickness. In addition, we compared the THz energy generated by OH1 crystal to 4-N,N-dimethylamino-4′-N′-methyl-4-stilbazolium tosylate (DAST) crystal using DFG, and we achieved 560 times higher energy using OH1 crystal than DAST crystal at around 1.1 THz.     

Design and analysis of a metallic waveguide with a DAST cap for continuously phase-matched terahertz difference frequency generation

We present a novel source for continuous terahertz (THz) wave generation using an organic ionic salt, 4-dimethylamino-N-methyl-4-stilbazolium-tosylate (DAST). THz waves are generated based on difference frequency generation (DFG) in the device. Phase matching condition and THz generation between 1.3 THz and 2.7 THz, for optical pump around 1.6 μm, are investigated. Our calculations predict that the device produces a relatively high THz output power of 11.07 μW from a 4 cm long waveguide at 2 THz.     

非线性有机材料DAST的研究及应用

随着光通信、光信息处理技术等的快速发展,非线性光学材料越来越受到学术界与工业的关注。与无机非线性光学材料相比,有机非线性光学材料具有响应时间短、易于加工和高非线性系数等优点。其中,4-(4-二甲氨基苯乙烯基)甲基吡啶对甲苯磺酸盐(DAST)是人工设计的一种具有非中心对称性和较强极化率的有机非线性材料。大量理论和实验结果表明,DAST具有高二阶光学非线性系数、高电光系数、大双折射率差和低介电常数等特性,能够产生更快、更强的光学非线性响应,还具有优异的太赫兹波发射及吸收性能,是目前综合性能最优、应用最广、最具研究价值的非线性有机材料。近年光谱研究显示,DAST还表现出各向异性的太赫兹光谱特性。文章系统地总结了DAST晶体在太赫兹波发射、二次谐波产生、电光探测和电光调制等众多领域的国内外研究成果,还概括了我们团队近期在DAST基薄膜、太赫兹光谱、光电特性、超材料等新领域的研究进展。此外,还提出将准相位匹配法用于DAST晶体研究、利用电场或自组装膜诱导生长DAST晶体等新思路。对DAST成果的总结和梳理,将促进非线性DAST有机材料在电光调制器、频率转换器、THz探测器等重要领域的应用与理论研究,使其能够更加广泛地应用在光通信、光信息处理、军事技术等重要领域。     

Terahertz generation with tandem seeded optical parametric generators

A simple difference frequency generation (DFG) scheme based on two seeded optical parametric generators is presented as a tunable terahertz (THz) source. Using the nonlinear optical crystal 4-dimethylamino-N-methyl-4-stilbazolium-tosylate (DAST) as the DFG crystal, our system has demonstrated continuous and seamless tunable operation from 1.6 to 4.5 THz. The output bandwidth of the THz source is 2.4 GHz. The utility of the source over this spectral range is demonstrated by measuring a high-resolution transmission spectrum of water vapor in air.     

Far-infrared properties of DAST

Using terahertz time-domain spectroscopy, we have measured the index of refraction and the absorption coefficient of the organic ionic salt 4-N, N-dimethylamino-4?-N?-methyl-stilbazolium tosylate (DAST). This promising organic electro-optic material exhibits strong absorption and dispersion for frequencies above 1 THz at both room temperature and 83 K. No reduction in the absorption strength is observed when DAST is cooled, suggesting a single-phonon origin of the resonances. A simple vibration of the anion and cation of the salt is suggested as the origin of the exceptionally strong far-infrared absorption and the high-frequency electro-optic properties of DAST.     

Narrow-band terahertz wave generation and detection in one periodically poled lithium niobate crystal

In this article, we present studies on therahertz (THz) wave generation and frequency up-conversion in a periodically poled lithium niobate (PPLN) crystal. A frequency at 1.37 THz was generated as femtosecond pump pulses passed through a PPLN crystal with grating periods of 30 μm. The pump-induced THz wave interacts with the probe wave in the crystal by frequency mixing. The frequency up-converted THz wave is easily detected by a normal photodiode. A new scheme for generation and detection of THz wave in one non-linear crystal was proposed.     

利用国内生长的有机晶体DAST作为THz源的研究

利用时域光谱技术分别测量了通过光整流法在国内新生长的有机晶体DAST和国际常用的高效能THz晶体ZnTe中产生的THz脉冲的时域光谱,也测量和分析了有机晶体DAST在THz波段的色散和吸收特性,并通过热辐射探测计(4.2 K Si-bolometer)测量了THz脉冲的绝对能量。结果表明,国内新生长的有机晶体DAST的确是一种高效率的THz产生晶体,优化生长条件后将可得到更高的产生效率。     

Tunable synchronously-pumped fiber Raman laser in the visible and near-infrared exploiting MOPA-generated rectangular pump pulses

We report a tunable synchronously pumped fiber Raman laser (SPFRL) in the near-infrared (NIR) and visible wavebands pumped by a pulsed, all-fiber PM 1060 nm master oscillator power amplifier (MOPA) and its frequency-doubled output, respectively. The seed was adaptively shaped to deliver rectangular output pulses, thereby enabling selective excitation of individual Raman Stokes lines. Using filtered synchronous feedback of the desired Raman Stokes line, the linewidth of the SPFRL was reduced by a factor of 4 and the extinction ratio of the desired Raman Stokes was improved by more than 3 dB relative to a simple single-pass conversion scheme. A continuous tuning range of 2.2 THz was obtained for each of the Raman Stokes orders in the visible (spanning from green to orange-first to fifth Stokes lines). A larger 5.0 THz tunable range was achieved in the NIR spectral region.