相转移催化法合成酰基偶氮化合物

偶氮类化合物是一类重要的化合物,被广泛地用作染料和分析试剂.在目前的信息时代,含有发色团的偶氮衍生物因具有光电导、光致变色等物理化学性能,特别是可能作为信息存贮及光电开关器件等高科技材料[1,2],已引起人们的极大兴趣和重视,但由于一般偶氮化合物作为高科技材料如光致变色记录材料,因存在记录保存的稳定性、反复擦写的耐久性、对半导体激光具有的吸光特性及存贮密度不理想等问题,而限制了它的使用.     

桥链七甲川菁的合成及光性能

菁是一种具有多功能用途的染料,除用作卤化银感光材料及有机光导材料的光谱增感剂、光记录材料中记录介质外,还可作为染料激光器中用的激光染料.我们曾合成了四甲川苯乙烯菁、五甲川(艹粦)及五甲川吡喃鎓等红外染料作为激光染料,测定了它们的光性能.本文合成了具有桥链的七甲川菁,研究了这些桥链七甲川菁的吸收光谱及荧光光谱,并以YAG激光倍频(532nm)作泵浦源,测定了它们的激光调谐范围、中心波长及激光转换效率.     

新型二维功能材料及衍生物的设计和制备

二维功能材料的制备方法常见的有以下几种:(1)机械剥离或液相剥离具有面间弱相互作用、面内强共价键合作用的层状材料生成单层或少数层的二维材料;(2)化学合成方法;(3)Langmuir-Blodgett单分子膜技术法;(4)层层自组装法;(5)化学气相沉积法;(6)分子束外延法和(7)原子层沉积技术法。这些材料及其有机-高分子衍生物具有独特的结构特征和优异的性质,在场效应晶体管、光调制器、锁模和Q开关激光、光限幅、信息和能源存储、射频器件、化学传感器等领域具有重要的潜在应用价值。近年来,除了众所周知的石墨烯外,其他诸如类石墨烯的无机纳米材料(六方氮化硼、过渡金属卤化物、石墨化氮化碳、层状金属氧化物等)、二维聚合物、金属-有机框架、钙钛矿、黑磷等二维材料也被广泛研究或探索。开发或探索更多二维材料应用的关键是设计和制备新颖的二维材料和它们的有机-高分子衍生物。在不久的将来,兼具规模经济和功能行为的二维材料化学的突破将极大地驱动新型二维材料应用领域的拓展。本文综述了二维材料的基本概念、研究进展、亟待解决的关键问题和未来的发展趋势。     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

<正>本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

<正>本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

<正>本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

N-(2-苦胺基乙基)单氮杂冠醚的合成

研究并比较了氮支套索型生色冠醚1a和1b两条不同的合成路线, 结果表明, 由N-苦基乙二胺(2)与1,11-二碘-3,6,9-三氧杂十一烷进行N-烷基化环化反应, 可方便地制备N-(2-苦胺基乙基)单氮杂-12-冠-4(1a), 但按此法未能获得更大环的-15-冠-5(1b);若从N-对甲苯磺酰基乙二胺(6)或N-(2-对甲苯磺酰胺基乙基)二乙醇胺(7)出发, 经环化, 脱除对甲苯磺酰基而制得的N-(2-氨基乙基)单氮杂冠醚5a和5b分别与苦基氯反应, 则可获得高产率的生色生色冠醚11a和1b.     

Synthesis of N-(4′-Benzo[15-crown-5])thiophenoxyphenylaminoglyoxime and its complexes with some transition metals

4-(Chloroacetyl)diphenyl thioether (1) was synthesized from chloroacetyl chloride and diphenyl thioether in the presence of AlCl₃ as catalyst in a Friedel-Crafts reaction. Subsequently, its keto oxime (2) and glyoxime (3) derivatives were prepared. N-(4′-Benzo[15-crown-5]thiophenoxyphenylaminoglyoxime (H₂L) and its sodium chloride complex (H₂L · NaCl) were prepared from 4-(thiophenoxy)chlorophenylglyoxime (3), 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Ni(II), Co(II) and Cu(II) complexes of H₂L and H₂L · NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF₂-capped Ni(II) mononuclear complex of the vic-dioxime was prepared. The macrocyclic ligands and their transition metal complexes were characterized on the basis of FT-IR, ¹H NMR, ¹³C NMR spectroscopy and elemental analyses data.     

N-对R苯基氮杂15冠5八钼多酸钠超分子配合物的合成与结构

为研究大环化合物对客体分子的选择性, 合成了通式为[NaL(Et2O)]2Na2Mo8O26的三种新型N-对R苯基氮杂15冠5八钼多酸钠超分子配合物(其中L分别为: N-苯基氮杂15冠5、N-对氯苯基氮杂15冠5和N-对甲苯基氮杂15冠5), 进行了元素分析, 红外光谱与核磁共振等结构参数的表征, 对R基为CH3的标题配合物作了X射线四圆衍射测定, 该晶体属单斜晶系, 空间群为P21/a,a=1.4590(4)nm, b=1.3817(3)nm, c=1.7639(5)nm, β=112.67(2)°, V=3.281(1)nm^3, Mr=2021.3, Dc=2.11g/cm^3,μ=2.37mm^-^1, F(000)=2048, R=0.045和Rw=0.057, 与[Na.(DB18C6)(CH3OH)M6O19和[Na(DB24C8)]2M6O19进行比较,结果表明: 大环化合物不仅对客体金属离子有分子识别性, 而且对与之抗衡的多酸阴离子也具有影响。     

Synthesis and structural diversity of barium (N,N-dimethylamino)diboranates

The reaction of a slurry of BaBr(2) in a minimal amount of tetrahydrofuran (THF) with 2 equiv of Na(H(3)BNMe(2)BH(3)) in diethyl ether followed by crystallization from diethyl ether at -20 °C yields crystals of Ba(H(3)BNMe(2)BH(3))(2)(Et(2)O)(2) (1). Drying 1 at room temperature under vacuum gives the partially desolvated analogue Ba(H(3)BNMe(2)BH(3))(2)(Et(2)O)(x) (1') as a free-flowing white solid, where the value of x varies from <0.1 to about 0.4 depending on whether desolvation is carried out with or without heating. The reaction of 1 or 1' with Lewis bases that bind more strongly to barium than diethyl ether results in the formation of new complexes Ba(H(3)BNMe(2)BH(3))(2)(L), where L = 1,2-dimethoxyethane (2), N,N,N',N'-tetramethylethylenediamine (3), 12-crown-4 (4), 18-crown-6 (5), N,N,N',N'-tetraethylethylenediamine (6), and N,N,N',N",N"-pentamethylethylenetriamine (7). Recrystallization of 4 and 5 from THF affords the related compounds Ba(H(3)BNMe(2)BH(3))(2)(12-crown-4)(THF)·THF (4') and Ba(H(3)BNMe(2)BH(3))(2)(18-crown-6)·2THF (5'). In addition, the reaction of BaBr(2) with 2 equiv of Na(H(3)BNMe(2)BH(3)) in the presence of diglyme yields Ba(H(3)BNMe(2)BH(3))(2)(diglyme)(2) (8), and the reaction of 1 with 15-crown-5 affords the diadduct [Ba(15-crown-5)(2)][H(3)BNMe(2)BH(3)](2) (9). Finally, the reaction of BaBr(2) with Na(H(3)BNMe(2)BH(3)) in THF, followed by the addition of 12-crown-4, affords the unusual salt [Na(12-crown-4)(2)][Ba(H(3)BNMe(2)BH(3))(3)(THF)(2)] (10). All of these complexes have been characterized by IR and (1)H and (11)B NMR spectroscopy, and the structures of compounds 1-3, 4', 5', and 6-10 have been determined by single-crystal X-ray diffraction. As the steric demand of the Lewis bases increases, the structure changes from polymers to dimers to monomers and then to charge-separated species. Despite the fact that several of the barium complexes are monomeric in the solid state, none is appreciably volatile up to 200 °C at 10(-2) Torr.     

Azacrown ethers containing oximic and Schiff base sidearms - potential heteronuclear metal ion receptors

A simple synthetic pathway for the preparation of oxime- and Schiff base-containing aza- and diazacrown ethers is reported. N-Methoxymethyl-substituted aza-15-crown-5 and aza-18-crown-6 as well as N,N′-bis(methoxymethyl)-substituted diaza-18-crown-6 were treated with 5-bromosalicylaldehyde to produce the N-(2′-hydroxy-3′-carbonyl-5′-bromobenzyl)-substituted aza-15-crown-5 (8), aza-18-crown-6 (9) and N,N′-bis(2′-hydroxy-3′-carbonyl-5′-bromobenzyl)-substituted diaza-18-crown-6 (10) compounds. Compounds 8 and 10 were treated with hydroxylamine to give oxime-substituted ligands 12 and 13. A series of bis-Schiff base-containing diaza-18-crown-6 ligands were prepared by reacting 10 with 2-hydroxyaniline (to form 14), 5-nitro-2-hydroxyaniline (15), 2-aminopyridine (16), 2-hydrazinopyridine (17) and N-aminomorpholine (18). Compounds 12–18 are potential complexing agents for simultaneous binding of soft transition and hard alkali or alkaline earth metal ions in one molecule. These new oxime- and Schiff base-containing ligands interacted strongly with Na⁺ and K⁺ in methanol. The interaction of the aromatic portions of 9, 10, and 12–15 with transition metal ions was shown by the UV spectra of the metal ion complexes in 50% aqueous DMF. The X-ray structure of 10 is reported.     

N-(2-对甲苯磺酰胺基乙基)单氮杂冠醚的合成及其晶体结构

N-对甲苯磺酰基乙二胺分别与1,11-二碘-3,6,9-三氧杂十一烷和1,14-二碘-3,6,9,12-四氧杂十四烷反应,制得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4或15-冠-5;当用N-(2-对甲苯磺酰胺基乙基)二乙醇胺与1,11-二对甲苯磺酸酯-3,6,9-三氧杂十一烷反应时,才能获得N-(2-对甲苯磺酰胺基乙基)单氮杂-18-冠-6.从甲醇溶液中培养得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4单晶,属单斜晶系,P2₁/a空间群;a=1.4229(1)nm,b=0.9595(2)nm,c=1.4564(1)nm,β=102.20(1)°,V=1.9435nm³,Z=4.最终偏离因子R=0.043.     

Iodide, azide, and cyanide complexes of (N,C), (N,N), and (N,O) metallacycles of tetra- and pentavalent uranium

In contrast to the neutral macrocycle [UN*(2)(N,C)] (1) [N* = N(SiMe(3))(3); N,C = CH(2)SiMe(2)N(SiMe(3))] which was quite inert toward I(2), the anionic bismetallacycle [NaUN*(N,C)(2)] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me(3)Si)NSiMe(2)CH(2)CH(2)SiMe(2)N(SiMe(3))] resulting from C-C coupling of the two CH(2) groups, and [NaUN*(N,O)(2)] (3) [N,O = OC(═CH(2))SiMe(2)N(SiMe(3))], which is devoid of any U-C bond, was oxidized into the U(V) bismetallacycle [Na{UN*(N,O)(2)}(2)(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN(3) or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN*(2)(N,C)(N(3))] [M = Na, 7a or Na(15-crown-5), 7b], M[UN*(2)(N,C)(CN)] [M = NEt(4), 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N(3))(2)] [M = Na, 9a or Na(THF)(4), 9b], [NEt(4)][UN*(N,N)(CN)(2)] (10), M[UN*(N,O)(2)(N(3))] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O)(2)(CN)] [M = NEt(4), 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral U(V) complex [U(N{SiMe(3)}SiMe(2)C{CHI}O)(2)I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined.     

One- or two-dimensional 2,3-naphtho crown ether complexes [Na(N15C5)]2[M(SCN)4] and [K(N18C6)]2[M(SCN)4] (M = Pd, Pt) constructed by pi-pi stacking interactions

Four novel 2,3-naphtho-15-crown-5 (N15C5) and 2,3-naphtho-18-crown-6 (N18C6) complexes [Na(N15C5)]2[Pd(SCN)4] (1), [Na(N15C5)]2[Pt(SCN)4] (2), [K(N18C6)]2[Pd(SCN)4] (3) and [K(N18C6)]2[Pt(SCN)4] (4) were synthesized and characterized by elemental analysis, FT-IR spectra and single-crystal X-ray diffraction. The structure analyses reveal that both 1 and 2 are assembled into zigzag chains by the strong intermolecular pi-pi stacking interactions between adjacent 2,3-naphthylene groups of N15C5. The molecules of complexes 3 and 4 are linked into 1D chains by the bridging K-O(ether) interactions between the adjacent [K(N18C6)]+ units and the resulting chains are constructed into a novel 2D network by inter-chain pi-pi stacking interactions between the neighboring 2,3-naphthylene moieties of N18C6. According to the supramolecular self-assemblies of complexes 1-4, two types of stacking model of naphthylene groups are given and discussed.     

冠醚硒菁染料的合成

合成了对称和非对称两个新的冠醚硒菁染料2,2'-二乙基-45,4'5'-双并-(15-冠-5)硒碳菁碘化季铵盐和2,2'-二乙基-4,5-并-(15-冠-5)硒碳菁碘化季铵盐以用三种新的中间体2,2'-二硝基-4,5,4',5'-双并-(15-冠-5)二苯基二硒化物, 2-甲基-5,6-并-(15-冠-5)苯并硒唑和2-甲基-3-乙基-5,6-并-(15-冠-5)苯并硒碘化季铵盐。报道了它们的红外、紫外、核磁共振、质谱数据。     

Synthesis of N- and S-Vinyl Derivatives of Heteroaromatic Compounds Using Phase-transfer Catalysis

A method has been developed for the synthesis of N- and S-vinyl derivatives of heteroaromatic compounds from NH heterocycles or their thiols in the phase-transfer catalytic system ClCH₂CH₂Br-KOH (s)-18-crown-6-toluene. It is shown that it is possible to prepare N,S-divinyl derivatives of 3-mercaptoindole and 2-mercaptobenzimidazole.