二腈基衍生物的合成及其光限幅性质

设计并合成了一系列含不同末端给电子基团及共轭链长度的1,1-二腈基-2,2-二苯基乙烯类化合物(D1-D7),用核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)和高分辨质谱(HRMS)对分子结构进行了表征.选用N,N-二甲基甲酰胺(DMF)为溶剂,测定了它们的线性光物理性质,用光漂白法研究了它们的光稳定性,用热失重法测试了它们的热稳定性.研究了这7个化合物针对800 nm脉冲激光(掺钛蓝宝石激光器,脉冲宽度~130 fs,重复频率1000 Hz)的光限幅性质.结果表明:以二烷基氨基为给电子基团的4个化合物(D4-D7)对800 nm的飞秒脉冲激光均具有显著的光限幅性能,限幅机制为双光子吸收(2PA),而端基给电子能力较弱、共轭链长较短的D1-D3光限幅效果并不明显.此外,D4-D7都具有较好的热稳定性和光稳定性.而且,该系列化合物的双光子吸收截面、光稳定性和热稳定性都具有随分子结构中给电子基团增强或共轭链增长而增大或提高的趋势.D7具有最好的综合性能,是一个有应用潜力的光限幅材料.     

六棱柱型金属团簇化合物W2Ag4S8(dppy)4的纳秒光限幅特性

新合成了一种金属团簇化合物W2Ag4S8(dppy)4,(分子式为C68H56Ag4N4P4S8W2)并用X-射线单晶衍射结构分析方法测定了其晶体结构.单晶X-射线衍射数据表明这种金属团簇化合物具有六棱柱型.在纳秒激光脉冲作用下研究了W2Ag4S8(dppy)4的二甲基甲酰胺(DMF)溶液的光限幅特性.实验结果表明W2Ag4S8(dppy)4的DMF溶液在放置一段时间后光限幅特性明显优于新配制的DMF溶液,其光限幅特性明显强于C60甲苯溶液,表现出其具有较强的光限幅特性.为了研究W2Ag4S8(dppy)4的光限幅机制及光限幅特性在放置一段时间后发生变化的原因,又做了非线性散射和泵浦探测实验,并对其光限幅机制和光限幅特性在放置一段时间后发生变化的原因进行了分析.     

四溴-2,3-萘酞菁铅的合成及性质研究

以1,8-二氮杂双环[5.4.0]+-碳烯-7(DBU)为催化剂合成了中心原子为重原子铅、环取代基为重原子溴的萘酞菁配合物四溴-2,3-萘酞菁铅[PbNcBr4],并研究了该配合物的电子吸收光谱、热稳定性、光限幅特性及重原子对其光限幅特性的影响及其机理.该配合物在近红外区(795～825nm)有强吸收(Q带),溴取代可使配合物Q带略微蓝移,溶剂的极性对配合物的电子吸收光谱有较大影响.该配合物具有较高的热稳定性,气氛对其热稳定性有明显影响,其在N2气氛中的热稳定性明显比在O2气氛中的高;在O2气氛中为一步分解,在N2气氛中为多步分解.标题配合物具有优异的非线性光限幅特性,在高线性透射率88%时的限幅阈值为148mJ/cm2,限幅幅值为332mJ/cm2,损伤阈值约为3J/cm2,其光限幅特性明显优于光限幅新材料C60(透射率70%时,限幅阈值大于240mJ/cm2).重原子铅和溴可显著优化材料的非线性光限幅特性.     

铜(Ⅱ)蛋氨酸席夫碱配合物EPR波谱研究

合成了邻香草醛蛋氨酸铜（Ⅱ）和2．4-二羟基苯甲醛蛋氨酸铜（Ⅱ）配合物，测定了它们在室温下多晶粉末EPR谱及室温和低温下不同溶剂中EPR谱，讨论了它们的成键特性，结果表明，这类配合物中，平面内σ配键和平面内π配键均起重要作用．     

四叔丁基四氮杂卟啉配合物的合成、热稳定性及光限幅特性研究

采用无金属四氮杂卟啉与金属盐回流的方法合成了2种四叔丁基四氮杂卟啉配合物，其中四叔丁基四氮杂卟啉铅(II)配合物未见文献报道。研究了该2种配合物及其配体的电子吸收光谱行为、热稳定性及在532 nm对8 ns激光的光限幅特性。结果表明：该类配合物的Q带的最大吸收峰值λ_max在570~630 nm之间，B带的最大吸收峰值λ_max在330~350 nm之间，随中心金属离子不同，Q带吸收峰位置有明显差异；配合物在氮气气氛中的起始分解温度大于250 ℃，其在热重图上的失重过程对应着4个取代基(-C(CH₃)₃)的脱去，共轭大环在500 ℃以下没有分解；它们的光限幅机制属于激发三重态的反饱和吸收(RSA)，其中四氮杂卟啉铅配合物具有更强的光限幅效应，这与铅的重原子效应有关。     

金属团簇MoS4Cu4(SCN)2(NC5H5)6的皮秒光学非线性特性和光限幅特性研究

由于激光技术的快速发展，新型超快可调谐波长的高功率激光器更多的在民用和军事上应用。快速的非线性光学器件的需求越来越多。近10年，人们投入大量研究寻找超快光学非线性材料，同时寻找快速响应、高线性透过率和低非线性透过率以及高损伤阈值的光限幅材料，研究发现金属酞菁化合物、金属卟啉化合物以及富勒烯衍生物具有良好的光限幅效果和强的光学非线性特性。     

不饱和脂环氮杂冠醚的合成和结构表征

采用相转移催化反应合成了两个不饱和脂环氮杂冠醚。利用红外光谱、核磁共振谱、质谱测定了他们的结构。特别是利用高分辨质谱、碰撞诱导裂解、质量分析离子动能谱对它们的质谱特性进行了深入研究,提出了可能的碎裂途径。 由于两个化合物的结构类似,所以它们的质谱有相同之处,但环大小和取代基不同,也有明显的差别。     

有机金属酞菁类化合物及其非线性光限幅特性

随着激光技术的快速发展,激光武器的性能也越来越优越,所造成的危害也越来越大,各国开始加大力度对激光防护材料进行研究.酞菁化合物具有限幅窗口宽、限幅效果明显、响应迅速等特点,是一类非常具有应用前景的光限幅材料.当前,制备出限幅性能好、稳定性强的酞菁光限幅材料成为激光防护材料领域中的研究热点.本文评述和总结了近几年在酞菁光限幅材料方面开展的系统研究工作,首先介绍了酞菁化合物实现光限幅效应的机制,并在此基础上详细分析了影响光限幅效应的因素以及光限幅器件化过程对酞菁光物理和光限幅性能的影响机理.根据分析结果提出了在基础和应用研究方面存在的科学问题,指出了该类型光限幅材料面临的挑战和今后的重要发展方向.     

四溴2,3-萘酞菁锌(Ⅱ)的合成及非线性光限幅特性

四溴萘酞菁锌;四溴2;3-萘酞菁锌(Ⅱ)的合成及非线性光限幅特性     

稀土硼氢化合物的研究(Ⅳ)——十氢十硼酸氧化吡啶合稀土(Ⅲ)配合物

合成了一类新的十氢十硼酸氧化吡啶合稀土(Ⅲ)配合物,其化学式为[Ln(PYO)_7]_2、(B_(10)H_(10))_3,式中Ln=Nd,Sm,Eu,Gd,Ho,Er,Tm,Yb;PYO=氧化吡啶。观测了配合物的一般性质以及它们的IR光谱、Raman光谱、UV光谱和摩尔电导率、TG-DTA图谱等特性,并探讨了它们的热行为。     

Supramolecular Complexes of Calix[4]resorcinolarene Tetramethylsulfonate with Organophosphorus Compounds

Supramolecular complexes of calix[4]resorcinolarene tetramethylsulfonate with certain organophosphorus compounds, such as dimethyl (1,1-dimethyl-3-oxobutyl)phosphonate, 1-O-[bis(N,N-diethylamino)thiophosphinoyl]-3,5-O-[(N,N-diethylamino)thiophosphonoyl)-2,4-O-methylenexylitol, and 2-O-[bis(N,N-diethylamino)thiophosphinoyl]-3,5-O-[(N,N-diethylamino)thiophosphonoyl)-1,4-anhydroxylitol, were prepared in aqueous and organic media. The complexes were isolated and characterized by elemental analysis and ¹H and ¹³C NMR spectroscopy.     

Synthesis, Characterization and Two-Photon Absorption Properties of a Novel Pyridinium Salt

A novel pyridinium salt, 2,4-bis[p-(N,N-dimethylamino)styryll-N-metlayl pyridinium iodide (BMSPI) was synthesized and characterized by TG, ^1H NMR spectroscopy and elemental analysis, and the reaction process was studied by using ES-MS. When BMSPI was pumped by a pulsed 1064 nm, 50 ps laser beam, it manifests highly efficient TPA (Two-Photon Absorption) and up-conversion superradiance. The up-conversion efficiency was 6.0% at the pump energy of 4-6 mJ and the lifetime of two-photon fluorescence was measured as 59 ps.     

苯乙烯相连的卟啉-三芳胺共轭体的合成及表征

以三芳胺甲醛和4-二乙氧基甲基苄基亚磷酸二乙酯为原料经Wittig-Horner反应制得化合物4-[4-(N,N-二苯胺基)苯乙烯基]苯甲醛, 4-[4-(N,N-二对甲苯胺基)苯乙烯基]苯甲醛和4-[4-(N,N-二对甲氧基苯胺基)苯乙烯基]苯甲醛, 这些化合物与吡咯在丙酸中回流得到一类通过苯乙烯相连的卟啉-三芳胺共轭体, 并采用¹H NMR, ¹³C NMR, MS及UV-vis对卟啉化合物的结构进行了表征.     

Two novel organic–inorganic hybrid materials from tetrachloridometallate(II) salts and 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium

Two organic–inorganic hybrid compounds have been prepared by the combination of the 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium cation with perhalometallate anions to give 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridocobaltate(II), (C₁₂H₁₂N₂)[CoCl₄], (I), and 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridozincate(II), (C₁₂H₁₂N₂)[ZnCl₄], (II). The compounds have been structurally characterized by single‐crystal X‐ray diffraction analysis, showing the formation of a three‐dimensional network through X—H...Cl_nM⁻ (X = C, N⁺; n = 1, 2; M = Co^II, Zn^II) hydrogen‐bonding interactions and π–π stacking interactions. The title compounds were also characterized by FT–IR spectroscopy and thermogravimetric analysis (TGA).     

Synthesis and Properties of a New Two-photon-absorbed Material Heasps

Abstract

A new dye Trans-4-[p-(N-hydroxyethyl-N-ethyiamino)styryl]-N-methylpyridinium p-toluene sulfonate (HEASPS) was synthesized, and the two-photon absorption (TPA), TPA-induced frequency up-conversion emission, and two-photon pumped (TPP) frequency up-converted lasing properties of this new dye were experimentally studied. This new dye has a moderate TPA cross-section of\sigma₂ = 4.7 × 10^?48 cm⁴ .s/photon at 1064nm, but exhibits a high lasing efficiency. The net conversion efficiency from the absorbed 1064 nm pump pulse energy to the 626 nm up-converted lasing energy is 18.2% at the pump energy level of 1.9 mJ.     

New fluorous ponytailed 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium halide salts

It is possible that fluorous compounds could be utilized as directing forces in crystal engineering for applications in materials chemistry or catalysis. Although numerous fluorous compounds have been used for various applications, their structures in the solid state remains a lively matter for debate. The reaction of 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridine with HX (X = I or Cl) yielded new fluorous ponytailed pyridinium halide salts, namely 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium iodide, C₈H₉F₃NO⁺·I⁻, (1), and 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium chloride, C₈H₉F₃NO⁺·Cl⁻, (2), which were characterized by IR spectroscopy, multinuclei (¹H, ¹³C and ¹⁹F) NMR spectroscopy and single‐crystal X‐ray diffraction. Structure analysis showed that there are two types of hydrogen bonds, namely N—H…X and C—H…X. The iodide anion in salt (1) is hydrogen bonded to three 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium cations in the crystal packing, while the chloride ion in salt (2) is involved in six hydrogen bonds to five 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium cations, which is attributed to the smaller size and reduced polarizability of the chloride ion compared to the iodide ion. In the IR spectra, the pyridinium N—H stretching band for salt (1) exhibited a blue shift compared with that of salt (2).     

New mesoionic systems of azolopyridine series 2. Synthesis,structures, and biological activity of 2-aminothiazolo[3,2-<Emphasis Type="Italic">a</Emphasis>]pyridinium salts and thiazolo[3,2-<Emphasis Type="Italic">a</Emphasis>]pyridinium 2-imidates

A new procedure was developed for the synthesis of 2-aminothiazolo[3,2-a]pyridinium salts 8 by the reaction of 2-halo-N-phenacylpyridinium salts with KSCN. The anion compositions of salts 8 were studied by ion chromatography. Acylation of salts 8 afforded representatives of the previously unknown bicyclic mesoionic thiazolo[3,2-a]pyridinium 2-imidate system 9. The three-dimensional structures of 2-amino-3-(p-bromobenzoyl)thiazolo[3,2-a]pyridinium thiocyanate and N-trifluoroacetyl-3-(p-nitrobenzoyl)thiazolo[3,2-a]pyridinium 2-imidate were established by X-ray diffraction analysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 226–232, January, 2005.     

Electron impact mass spectrometry of isomeric [(5-N-methyl) and (12-N-methyl)]-11-(o- and p-R-aniline)-5H-dibenzo [b,e] [1,4]diazepines

The mass spectra of twelve isomeric [(5-N-methyl) and (12-N-methyl)]-11-(o- and p-R-aniline)-5H-dibenzo [b, e] [l,4]diazepines which have potentially useful pharmacological properties are presented.     

Synthesis and structures of pyridoannelated 1,2,3,4-tetrazine 1,3-dioxides

Treatment of 2- and 4-amino-3-(tert-butyl-NNO-azoxy)pyridines with nitrating agents (N₂O₅or NO₂BF₄) afforded the first representatives of pyridoannelated 1,2,3,4-tetrazine di-N-oxides, viz., pyrido[2,3-e][1,2,3,4]tetrazine 1,3-dioxide (9), 7-nitropyrido[2,3-e][1,2,3,4]tetrazine 1,3-dioxide (10), and pyrido[3,4-e][1,2,3,4]tetrazine 2,4-dioxide (11). These compounds were studied by ¹H, ¹³C, and ¹⁴N NMR spectroscopy. The 1:1 complex of compound 10 with benzene was studied by X-ray diffraction analysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2471–2477, November, 2004.     

Synthesis of Some New 3-Oxo-2-[(Z)-1-phenylmethylidene]-5H-[1,3]thiazolo[3,2-a]-and N-Acetylated Pyrimidines

3-Oxo-2-[(Z)-1-phenylmethylidene]-5H-[1,3]thiazolo[3,2-a] pyrimidine derivatives 2a–f were synthesized by the reaction of an appropriate 3,4-dihydro-2(H)-pyrimidone 1 , chloroacetic acid, sodium acetate and benzaldehyde. Reaction of 1 with acetic anhydride under heating afforded only 3-N-acetylated 3,4-dihydro-2(H)-pyrimidines 3a–f . The yields of the products after recrystallization from ethanol were of the order of 60–92 %. IR, ¹ H NMR spectroscopy, and elemental analysis were used for the identification of these compounds.