铽多元配合物的合成及其性质研究

通过铽金属醇盐与丙烯酸、β二酮配体反应,合成了4种具有聚合活性的含铽配合物单体,通过元素分析红外光谱、紫外光谱,确定了它们的组成和结构。热分析表明,这些铽配合物单体没有熔点,起始分解湿度在190－200℃之间。在溶液及状态下研究了这些含铽多元配合物的荧光性质,在紫外光激发下,它们均能发射铽离子的特征荧光,溶剂的极性和配体的三线态能级会影响它们的光强度;粉末状态下,这些铽多元络合物的荧光单色性较好。     

含铽配合物的合成及其荧光性研究

采用稀土铽金属醇盐与丙烯酸、乙酰丙酮、中性配体(邻菲啰啉或联吡啶）反应，在非水介质下合成具有高聚合活性的含铽配合物单体，通过元素分析、红外光谱、紫外光谱确定了它们的组成和结构，合成的铽配合物单体溶于一般的有机溶剂并能强烈吸收紫外光谌芤杭胺勰┳刺卵芯空庑┑ヌ宓挠庑浴T谧罴鸭し⒉ǔは拢蔷芊⑸滹胱拥奶卣饔猓ド越虾谩Q返淖刺叭芗恋募远耘浜衔锏牡ヌ宓挠庑杂薪洗笥跋欤行耘涮辶诜茊⒘拎さ囊芴岣咚堑挠夥⑸淝慷取     

Synthesis and Properties of Sulfophenyl-Substituted Metal Phthalocyanine Complexes

Sulfonation of 4-phenylphthalic acid gave 4-(p-sulfophenyl)phthalic acid triammonium salt which was used in the synthesis of tetra[4-(p-sulfophenyl)]phthalocyanine copper and cobalt complexes by the urea method. The products were characterized by elemental analyses and ¹³C NMR, IR, and electronic spectra. Some specific features of the electronic spectra of sulfophenyl-substituted metal phthalocyanines were revealed, depending on the central metal atom, solvent nature, and concentration.     

两个磷光铱配合物的合成和性质研究

由于具有P=O键,二（二苯基膦酰）胺（tetraphenylimidodiphosphinateacid,Htpip）作为辅助配体引入Ir（Ⅲ）配合物中,可以提高配合物的电子迁移率和器件的效率。采用氟取代的2-（4-氟苯基）吡啶（F₄-ppy）为主配体、以Htpip和三氟甲基取代的Htfmtpip为辅助配体合成了2个铱配合物Ir（F₄-ppy）₂（tpip）和Ir（F₄-ppy）₂（tfmtpip）。晶体结构中Ir原子的配位几何构型均为八面体构型,Ir（F₄-ppy）₂（tpip）属于正交晶系Pbca空间群,而Ir（F₄-ppy）₂（tfmtpip）属于单斜晶系P2₁/c空间群。配合物都具有较好的热稳定性,Ir（F₄-ppy）₂（tpip）和Ir（F₄-ppy）₂（tfmtpip）的初始分解温度分别为385和395℃。配合物Ir（F₄-ppy）₂（tfmtpip）的氧化和还原峰较配合物Ir（F₄-ppy）₂（tpip）分别向正电压移动了大约0.134和0.12V,相应的HOMO和LUMO能级分别降低了0.14和0.43eV。在室温、1×10^-5mol·L^-1的CH₂Cl₂溶液中Ir（F₄-ppy）₂（tpip）和Ir（F₄-ppy）₂（tfmtpip）的最大磷光发射峰分别位于492和495nm,量子效率分别为9.2%和16.4%。结果表明在辅助配体上引入4个三氟甲基后不仅可以提高配合物的热稳定性和电化学稳定性,并且可以调控配合物的HOMO/LUMO能级和发光效率。     

Synthesis and Photophysical Properties of T-Shaped Coinage-Metal Complexes

The photophysical properties of a series of T-shaped coinage d¹⁰ metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new example of a tridentate T-shaped Ag^I complex. Post-complexation modification of the Au^I complex provides access to a linear cationic Au^I complex following ligand alkylation, or the first example of a cationic square planar Au^III−F complex from electrophilic attack on the metal centre. Emissions ranging from blue (Cu^I) to orange (Ag^I) are obtained, with variable contributions of thermally-dependent fluorescence and phosphorescence to the observed photoluminescence. Green emissions are observed for all three gold complexes (neutral T-shaped Au^I, cationic linear Au^I and square planar cationic Au^III). The higher quantum yield and longer decay lifetime of the linear gold(I) complex are indicative of increased phosphorescence contribution.     

Synthesis and Properties of meso-Phenyl-Substituted Tetrabenzoazaporphins Magnesium Complexes

Magnesium complexes of highly soluble meso-phenyl-substituted tetrabenzoazaporphins were prepared from 1,3-diiminoisoindoline and phenylacetic acid in the presence of magnesium oxide. Some physicochemical and spectral properties of the compounds were investigated.     

Synthesis and Properties of Cross-Linked 4-Vinylpyridine-Styrene-Halogen Complexes

Cross-linked 4-vinylpyridine-styrene beads (PVPS) containing various amounts of pyridine rings were synthesized and reaction with methyliodide and peroxyacetic acid gave corresponding N-methylpyridinium salts and N-oxides with more than 92% of the pyridine rings being transformed. PVPS formed stable complexes with bromine and chlorine in the ratio 1:1, and when a higher amount of halogen was used, complexes with two molecules of halogen on each pyridine were formed. Similar complexes were also formed with PVPS-N-oxides in the presence of bromine and chlorine, while the reaction of PVPS-hydrohalide with bromine and chlorine resulted in hydrobromide perbromide and hydrochloride perchloride resins. The chemical activity of halo-substituted resins was tested in the reaction with 1,1-diphenylethylene. Chi or o-substituted resins are very stable, while bromo-substituted beads gave bromoalkene, dibromide, and alkoxybromide, depending on the structure of the reagent, solvent, and reaction temperature.     

Salen型化合物的合成、表征及性质

设计合成了两种新型Salen配体H2L1(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二甲氧基-1,2-苯二胺)、H2L2(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二硝基-1,2-苯二胺)及相应的镍、铜、锌金属配合物ML1、ML2(M=Ni,Cu,Zn),并分别采用核磁共振(1HNMR)波谱、紫外-可见(UV-Vis)吸收光谱、红外(IR)光谱、质谱(MS)和元素分析进行了表征.探究了配体及其配合物的荧光性质.研究发现,与H2L1相比,配体H2L2由于引入强的吸电子基团―NO2,其荧光强度减弱.相对于配体,锌离子的配位则导致其配合物的荧光强度增强,而镍和铜离子的嵌入则使得配合物ML1、ML2(M=Ni,Cu)荧光猝灭.对电化学性质的研究表明,CuL1的氧化还原过程为准可逆的单电子过程;与H2L2相比,配体H2L1由于引入强的给电子基团―OCH3,其溶液的导电性降低.     

两个磷光铱配合物的合成和性质研究

由于具有P=O键,二(二苯基膦酰)胺(tetraphenylimidodiphosphinate acid,Htpip)作为辅助配体引入Ir(III)配合物中,可以提高配合物的电子迁移率和器件的效率。采用氟取代的2-(4-氟苯基)吡啶(F4-ppy)为主配体、以Htpip和三氟甲基取代的Htfmtpip为辅助配体合成了2个铱配合物Ir(F4-ppy)2(tpip)和Ir(F4-ppy)2(tfmtpip)。晶体结构中Ir原子的配位几何构型均为八面体构型,Ir(F4-ppy)2(tpip)属于正交晶系Pbca空间群,而Ir(F4-ppy)2(tfmtpip)属于单斜晶系P21/c空间群。配合物都具有较好的热稳定性,Ir(F4-ppy)2(tpip)和Ir(F4-ppy)2(tfmtpip)的初始分解温度分别为385和395℃。配合物Ir(F4-ppy)2(tfmtpip)的氧化和还原峰较配合物Ir(F4-ppy)2(tpip)分别向正电压移动了大约0.134和0.12 V,相应的HOMO和LUMO能级分别降低了0.14和0.43 eV。在室温、1×10-5mol·L-1的CH2Cl2溶液中Ir(F4-ppy)2(tpip)和Ir(F4-ppy)2(tfmtpip)的最大磷光发射峰分别位于492和495 nm,量子效率分别为9.2%和16.4%。结果表明在辅助配体上引入4个三氟甲基后不仅可以提高配合物的热稳定性和电化学稳定性,并且可以调控配合物的HOMO/LUMO能级和发光效率。     

Synthesis and Properties of meso-Alkyltetrabenzotriazaporphyrins and Their Zinc Complexes

1,3-Diiminoisoindoline was reacted with aliphatic carboxylic acids in the presence of zinc oxide to obtain a mixture of meso-alkyl-substituted tetrabenzoazoporphyrins, from which zinc complexes of meso-alkyltetrabenzotriazaporphyrins were isolated.     

Conducting and Photoactive Polymers on the Basis of Transition Metal Complexes: Electrochemical Synthesis

Mechanism of electrochemical oxidative polymerization and formation of polymers based on the transition metal complexes are considered. The complexes under study are assumed to have the resonance structures and a highly reactive imino group (–N=CH–) in the macrocyclic ring. IR spectra of the bis(salicylidene)ethylenediamine ligand (H₂Salen), [NiSalen] and [PdSalen] monomers, and the respective polymers are examined and used for the experimental substantiation of the proposed mechanism underlying the formation of conducting polymers.     

Synthesis and Electro-optical Conducting Properties of Disperse Red 1 Functionlized Polymethylphenylsilane

Polymethylphenylsilane (PMPS) was modified by chloromethylation then condensed with Na salt of Disperse Red 1(DR1). The product, DR1 functionlized PMPS(PMPS-DRD, was thoroughly washed until it had no DRl or other dopant. Its glass transition temperature is 155℃, contains 4.5% weight of DRl residue. The UV-Vis spectrum of PMPS-DRl shows a broad ab-sorption band in the range 400-700 nm. Photoconductivity measured on a 2 μm film made of PMPS-DR1, using a 632.8 nm He-Ne laser beam, shows that it is electric field dependent and in the range of 10^-13 to 10^-11S/cm. The electro-optical coefficient of PMPS-DRl was measured as a value of r₃₃=0.8 pm/V.     

复合酸掺杂导电聚苯胺的合成及性能

采用复合酸掺杂微乳液法合成导电聚苯胺. 探讨了反应温度和掺杂剂质量比对聚苯胺性能的影响,并通过四探针、塔菲尔曲线、激光粒度分析、热重分析以及红外光谱测试技术,对聚苯胺进行了研究与表征. 结果表明,当聚合温度为15 ℃、磺基水杨酸和十二烷基苯磺酸钠的质量比为2.5∶1时,掺杂态聚苯胺电导率和溶解度达到最大值,同时具有良好的防腐蚀能力;其中电导率可达11 S/cm,在氮甲基吡咯烷酮(NMP)中溶解度可达85%;经电化学工作站测试的塔菲尔曲线可知,其腐蚀电位为-0.391 V. 热重分析表明,复合酸掺杂聚苯胺热分解温度约为440 ℃;粒径分析表明,约有90%的聚苯胺颗粒集中在50～100 nm之间.红外光谱表明,复合酸掺杂聚苯胺各主要吸收峰均向低频方向移动,说明掺杂的有效性.     

二乙基姜黄素稀土配合物的合成及其光学性质

以乙醇为溶剂,用姜黄素、溴乙烷和稀土盐等为原料,合成了二乙基姜黄素镧(Ⅲ)和钐(Ⅲ)配合物,通过IR,1HNMR,MS和元素分析对目标化合物进行了结构表征;并对它们的紫外可见电子光谱、单、双光子荧光光谱进行了研究,同时采用1064nm皮秒脉冲激光通过Z扫描技术拟合得到了双光子吸收系数和吸收截面.结果显示目标物具有较好的光学性质和双光子吸收截面.     

手性双核Salen配合物的合成与谱学性质

Six novel chiral dinuclear Salen complexes [Cu₂L₁·H₂O (3a), Cu₂L₂(3b), Ni₂L₁·2H₂O (4a), Ni₂L₂(4b), Mn₂Cl₂L₁·H₂O (5a), Mn₂Cl₂L₂ (5b)] have been synthesized(L₁ and L₂ are chiral dimeric Salen ligands with different chain length which were synthesized from (R,R)-diaminocyclohexane, salicylaldehyde, 4,4′-(1,10-decaneoxy)salicylaldehyde, 4,4′-(1,6-hexyloxy)salicylaldehyde). These compounds were charactered by elemental analysis, ¹H NMR, FT-IR, UV-Vis and CD spectra. The FT-IR, UV-Vis and CD spectra were discussed and compared with those of monomeric ligand and complex in detail. It was found that the spectra properties of compounds of different chain length were almost alike, and the properties of dimeric and monomeric compound were similar too. Furthermore Cotton effect and Cotton split of CD spectra of these chiral compounds were explained by the exciton interaction theory. It seemed that the direction of Cotton split depend on the configuration of diaminohexane. (R,R)-diaminohexane determine the chirality of Salen compounds as negative, and the positive and negative component of Cotton split lie at higher and lower energy respectively.     

两种甲氧基苯基咔咯铜配合物的合成及光谱性质

合成了两个中位苯基上具有甲氧基取代基的铜咔咯配合物(Tp-OCH3PC)Cu和(To,p-(OCH3)2PC)Cu,通过紫外-可见、红外光谱、元素分析、核磁共振及质谱对它们进行了表征。研究了配合物在非水溶剂中的电子顺磁共振、电化学和光谱电化学性质,结果表明无论在固体状态还是在非水溶剂中,配合物的中心金属离子均为三价铜Cu(Ⅲ),在给定的溶剂中Cu(Ⅲ)可以发生可逆的还原反应生成Cu(Ⅱ),也可以被可逆氧化为Cu(Ⅲ)的阳离子自由基。探讨了甲氧基取代基以及溶剂对配合物的紫外-可见光谱和氧化还原电位的影响。     

聚合物稀土配合物发光材料的合成与性能研究

聚合物稀土配合物兼具稀土离子独特的发光特性和聚合物易加工成型等优点,在平面显示和信息通讯等领域具有巨大的应用潜力,研究开发新型大分子配体以及稀土含量高且荧光强的聚合物稀土配合物材料具有重要意义。本文重点对聚合物稀土配合物发光材料结构设计和合成方法的研究进展进行了综述,并从大分子配体和高分子稀土配合物的结构与发光性能关系...     

反应型三元铽配合物的合成及发光性能研究

以邻菲咯啉为第一配体，顺丁烯二酸酐、丙烯腈、十一烯酸、油酸、亚油酸为活性第二配体，合成了5种新的反应型三元铽配合物。通过元素分析，EDTA配位滴定分析，红外、紫外、荧光光谱分析，对标题配合物的组成、结构进行了表征，并研究了它们的发光性能。结果表明，五种新的反应型三元配合物与相应的二元配合物相比发光强度大大提高，且配合物中引入了能与其它单体共聚的活性第二配体，为合成具有优异发光性能的键合型稀土高分子功能材料提供了一条新的途径。     

镧系1：10系列钼钒杂多配合物的合成与性质

报道用一步酸化法制得四种未见报道的１：１０系列镧系钼钒杂多配合物Ｋ７Ｈ８ＬｎＭｏ４Ｖ６Ｐ３６．ｘＨ２Ｏ（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ）。提示元素分析，红外光谱，紫外光谱，Ｘ射线粉末衍射及差热－热重分析结果讨论了它们的结构及性质。     

Synthesis and Properties of Copper Trimesinate Complexes with Polypyridine Ligands

Russian Journal of General Chemistry - Copper trimesinate complexes Cu3(BTC)2L3 and Cu3(BTC)2L with polypyridine ligands, such as 2,2′-bipyridyl, 1,10-phenanthroline, and...