配合物Eu(Sal)2(phen)2(NO3)的合成及荧光性能的研究

用硝酸铕、水杨酸与邻菲罗啉为原料合成了配合物Eu(Sal)2(phen)2(NO3),考察了配体用量和溶剂用量等因素对反应的影响.通过元素分析、红外光谱和紫外光谱确定了配合物的组成及结构,并通过荧光光谱对其荧光性质进行了研究.     

配合物Eu(Sal)2(phen)2(NO3)的合成及荧光性能的研究

用硝酸铕、水杨酸与邻菲罗啉为原料合成了配合物Eu(Sal)2(phen)2(NO3),考察了配体用量和溶剂用量等因素对反应的影响.通过元素分析、红外光谱和紫外光谱确定了配合物的组成及结构,并通过荧光光谱对其荧光性质进行了研究.     

功能含氮配合物[M(bpt)_2(H_2O)_4]·2H_2O(M=Zn、Co、Cd)的合成表征及荧光性质

采用界面合成的方法,以3,5-二(4-吡啶基)-1,2,4-三唑(Hbpt)和乙酸盐为原料合成了标题配合物,通过X-射线单晶衍射、元素分析、红外光谱、荧光光谱等技术对合成配合物进行了结构测定和性质表征。结果表明,配合物均属于同构物质,均为单斜晶系,P121/c空间群。固体状态的荧光性质测定表明,配合物均具有较强的荧光性质。     

配合物Nd_2(C_4H_2O_4)·(C_(10)H_2O_8)_(1.5)·2H_2O的合成及其光电性能的研究

采用水热法合成了顺丁烯二酸和均苯四甲酸二酐与稀土钕的配合物。通过元素分析、红外光谱、紫外光谱、荧光光谱、循环伏安、热重分析等对其进行了表征。室温下的荧光光谱表明,配合物在453.0nm处具有很强的发射峰。电化学性质研究表明,配合物在-0.15~0.15V(vs.SCE)电位范围内具有明显的电化学活性。     

N-(2-羟苄基)-DL-丙氨酸铕(Ⅲ)配合物的合成及荧光性质

以发光的三价铕离子为中心体,N-(2-羟苄基)-DL-丙氨酸(H2sala)和1,10-邻菲咯啉(phen)为配体,在混合溶剂中合成了二元铕配合物[Eu(sala)(H2O)4].Cl和三元铕配合物[Eu(sala)(phen)2].Cl。通过元素分析、摩尔电导、红外光谱和热重分析等手段确定了配合物的组成及结构。荧光光谱数据表明,三元配合物的荧光强度高于二元配合物。     

Eu(DMBM)_2(2,2′-bipy)NO_3的合成与荧光光谱

本工作首次合成了Eu(DMBM)_2(2,2′-bipy)NO_3(DMBM=二对甲氧基苯甲酰甲烷,2,2′-bipy-2,2′-联吡啶)。通过元素分析、热谱、电导率、红外和拉曼光谱、质子核磁共振谱对所合成化合物进行了表征。在77K测定了固体配合物的激发光谱和发光光谱。光谱数据说明配合物含有两种Eu(Ⅲ)格位。配合物中三种配体在Eu(Ⅲ)周围的分布情况略有不同,显示出不同的晶体场效应。光谱数据表明,配合物中Eu(Ⅲ)格位属于非中心对称的点群C_1或C_3或C_2。     

新型配合物[Cu_2(phen)_2(OH)_2(H_2O)_2][Cu_2(phen)_2(OH)_2Cl_2]Cl_2·6H_2O的合成与性质研究

采用溶液法合成了分子式为[Cu2(phen)2(OH)2(H2O)2][Cu2(phen)2(OH)2Cl2]Cl2.6H2O的配合物。通过元素分析、红外光谱、紫外光谱和X-射线单晶衍射对配合物进行了表征;此外,还对该配合物进行了非等温热分解动力学研究。研究表明,配合物中有两组双核配位单元,分别为[Cu2(phen)2(OH)2(H2O)2]2+和[Cu2(phen)2(OH)2Cl2];两个配位单元的中心原子铜均为五配位的,具有扭曲的四方锥结构,配合物通过氢键作用形成超分子结构。此配合物的热分解反应是分两步进行的,第一步反应的动力学方程为dαdT=Aφ.exp-E()R T3/2[(1-α)43(1-α)-13-]1-1,活化能E=151.8kJ/mol,指前因子lgA=16.9435;第二步反应的动力学方程为dαdT=Aφ.exp-E()R T32[(1-α)43(1-α)-13-]1-1,活化能E=201.5kJ/mol,指前因子lgA=7.5447。     

配位聚合物[Co(BZM)_2(TMBA)_2]_n的合成和表征

常温条件下在水和乙醇混合溶剂中,由苯并咪唑(BZM)、2,4,6-三甲基苯甲酸(HTMBA)与金属离子Co(Ⅱ)合成了1个新颖的三维超分子配合物[Co(BZM)2(TMBA)2]n,并通过X-射线单晶衍射、元素分析、红外光谱以及热稳定性分析等对其进行了结构测定和表征。分析表明,该配合物属正交晶系,Pbca空间群,中心金属离子Co(Ⅱ)是六配位,由4个氧原子和2个氮原子包围,氧原子分别来自2个2,4,6-三甲基苯甲酸分子,氮原子分别来自2个苯并咪唑分子。配合物通过范德华力形成3D网络结构。     

稀土配合物[Ln_2(sba)_3(phen)_2(H_2O)_2](Ln=Eu,Tb)合成、表征和性质研究

在乙醇和水的混合溶剂中,利用辛二酸[Suberic acid=H2sba]、邻菲罗啉(Phen)合成了标题化合物,通过化学分析、元素分析、红外光谱、热分解等方法对配合物组成进行了分析和表征,并研究了两种配合物的荧光性质。     

配合物[Cd_2(1,2-pda)_2(2,2′-bipy)_2(H_2O)_2]_n的合成、晶体结构与荧光性质

在水热条件下利用邻苯二乙酸,2,2′-二联吡啶和硝酸镉反应生成配合物[Cd_2(1,2-pda)_2(bipy)_2(H_2O)_2]_n(1,2-pda=邻苯二乙酸、2,2′-bipy=2,2′-二联吡啶)。采用红外光谱、差热-热重、C H N元素分析、荧光及单晶X射线衍射等手段对晶体结构进行了表征。配合物属正交晶系,空间群为Pna2(1);晶体学参数:a=18.5087(18)nm,b=8.9432(9)nm,c=23.685(2)nm;α=β=γ=90。其基本结构单元由两个Cd(II)原子、两个邻苯二乙酸根、两个2,2′-二联吡啶、两个水分子组成。邻苯二乙酸与Cd(Ⅱ)原子交替连接形成一维直线,相邻的两条直线通过氢键的支撑连接形成一维双链结构。荧光性质研究表明,配合物在504nm处呈现较强的荧光发射(λ_(ex)=350nm)。     

四元混配配合物[Ln(x-MBA)2(NO3)(Phen)]2的合成及表征

在酸性介质,乙醇／水混合溶剂中合成得到了三个系列的四元混配配合物[Ln(x-MBA)2(NO3)(Phen)]2(Ln=La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Er;MBA=CH3C6H4COO^-）。用元素分析、IR、UV、DTA－TG和^1H NMR等方法对配合物进行了表征,测量了三个Eu配合物的荧光光谱和三个Gd配合物的ESR谱。     

2-氨基嘧啶超分子配合物[Cu(2-AP)2(NO3)2]的合成与晶体结构

以2-氨皋嘧啶缩水杨醛席夫碱和硝酸铜为原料,在常温下,用甲醇和水为溶剂合成了配合物[Cu（2,Ap）2（NO3）2]（2-Ap=2,氨基嘧啶）。通过红外光潜、元素分析、X-射线单品衍射对它进行了结构解析和表征,并系统研究了配合物的结构特点。     

PLFX-Co(phen)_3~(2+)复合物与CT-DNA的结合性质及切割活性

利用荧光光谱及流体动力学等方法,研究了普利沙星(PLFX)-Co(phen)32+与CT-DNA间的作用机理。荧光光谱测量结果表明:普利沙星和Co(phen)32+发生了结合作用形成了复合物,配比为2∶1;向PLFX-Co(phen)32+体系中,加入CT-DNA后,复合物进一步与DNA相结合,结合常数为2.18×105L/mol。通过粘度法、熔点测定及凝胶电泳实验研究了复合物与CT-DNA的相互作用。结果表明体系与CT-DNA间主要是沟槽作用;PLFX-Co(phen)32+能够有效切割质粒DNA。     

Synthesis,Characterization and Fluorescence Properties of Poly(styrene-co-n-caprylamide maleic acid) and Its Europium(III) and Terbium(III) Complexes

Copolymer of poly(styrene-co-n-caprylamide maleic acid) (PSCMA, defined as HL) and its lanthanide complexes Ln(L)₃·6H₂O (Ln = Eu and Tb) had been synthesized and characterized by elemental analysis, X-ray diffraction, Fourier transform infrared spectra, UV-spectrophotometer and thermal analysis (TG–DTA). The fluorescence properties of the HL ligand and the Ln(L)₃·6H₂O complexes in the solid state were investigated. At room temperature, the HL ligand had a strong broad emission band at 410–575 nm (λmax = 458 nm) under excitation at 380 nm, while the respective characteristic emission of Eu(III) and Tb(III) ions was observed in Ln(L)₃·6H₂O complexes. This demonstrated that the HL ligand in the extra-framework channels succeeded in sensitizing Eu(III) and Tb(III) ions emission. Compared with the Eu(L)₃·6H₂O complex, the fluorescence intensity of the Tb(L)₃·6H₂O complex was much stronger. This indicated that the lowest excited triplet state energy level of HL matched well with the excited state energy level of Tb(III). With the increase of the Ln(III) ions content below 15 wt%, the fluorescence intensity increased monotonically. All the Ln(L)₃·6H₂O complexes exhibited high quantum yield, long fluorescence lifetime and good thermal stability.     

Distinct composite structure and properties of Eu(phen)2Cl3(H2O)2 in poly(methyl methacrylate) and polyvinylpyrrolidone

The luminescent europium complex Eu(phen)₂ Cl₃(H₂O)₂ (phen refers to 1,10‐phenanthroline) was doped in poly(methyl methacrylate) (PMMA) and polyvinylpyrrolidone (PVP), respectively. The formed composite systems with different molar ratios of C?O groups in polymers and Eu ions were characterized by X‐ray diffractometry (XRD), FTIR, and photoluminescent (PL) spectroscopy and lifetime measurement. The XRD diffractograms show that the composites of PMMA/Eu(phen)₂Cl₃(H₂O)₂ and PVP/Eu (phen)₂Cl₃(H₂O)₂ have crystalline and amorphous structures, respectively, arising from different interactions between the polymers and the complex, as revealed by FTIR spectra. This leads to distinct luminescent characteristics arising from the ⁵D₀→⁷F_J transitions of Eu(III) ion (J = 0–4). For the composite systems of PMMA/complex, the characteristics of the emission lines change with decreasing molar ratios of C?O/Eu and approach that of the pure complex; whereas the composite systems of PVP/complex have similar spectral features, regardless of the molar ratios, differing from that of the pure complex. The polymer matrices have a substantial influence on the structure and properties of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3524–3530, 2004     

Study on interaction between Eu(III) and thermosensitive microsphere

Based on the synthesis of poly(N-isopropylacrylamide)-grafted poly(N-isopropylacrylamide-co-styrene) (PNNS) microsphere, Eu(III) was chosen to coordinate with PNNS. The interaction between Eu(III) and PNNS was characterized by using X-ray photoelectron spectroscopy, Fourier transform infrared, ultraviolet–visual and fluorescence spectroscopy. The results from experiments indicated that the Eu(III) is mainly bonded to O of the carbonyl groups of PNNS and formed the complex of PNNS–Eu(III). After forming the PNNS–Eu(III) complex, the emission fluorescence intensity of Eu(III) in the complex is significantly enhanced because the effective intramolecular energy-transfer from PNNS to Eu(III). Especially, the maximum emission intensity of the PNNS–Eu(III) complex at 614 nm is enhanced about 33 times comparing to that of the pure Eu(III). The intramolecular energy-transfer efficiency from PNNS to Eu(III) reaches 55%.     

配合物Zn(3-apac)2(H2O)2的合成与表征

以3-氨基吡嗪-2-羧酸为配体合成了一个锌的单核配合物Zn(3-apac)2(H2O)21(3-apac:3-氨基吡嗪-2-羧酸),并利用元素分析,红外光谱,单晶X-射线衍射以及热重分析对配合物1进行了表征.晶体学数据:单斜晶系,C2/c空间群,a=0.79137nm,b=1.26517nm,c=1.3631nm,α=...     

Multi stimuli-responsive HPC-PAA/Eu(AA)3Phen complex nanogels and their decoration with 3-APBA for detecting glucose

In this paper, novel multi stimuli-responsive complex nanogels of hydroxypropylcellulose (HPC)-PAA/Eu(acrylic acid [AA])₃Phen were synthesized by radical polymerization method with HPC, rare earth complex (Eu(AA)₃Phen) and AA as raw materials, and the 3-aminophenylboronic acid (3-APBA) decorated nanogels (HPC-PAAPBA/Eu(AA)₃Phen) were fabricated via condensation of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride with 3-APBA. The microstructure, morphology and diameter of the nanogel were characterized by Fourier transform infrared spectrometer, UV–Visible spectrophotometer, transmission electron microscope, dynamic light scattering. Moreover, the fluorescence responsive performance of complex nanogels to temperature, pH value and glucose concentration was investigated by photoluminescence spectroscopy. The results showed that both of the as-prepared nanogels were uniform in size and had good monodispersity. The temperature and pH value had significant effects on the particle size and the fluorescence emission intensity of the HPC-PAA/Eu(AA)₃Phen complex nanogels; after decoration with 3-APBA, the obtained HPC-PAAPBA/Eu(AA)₃Phen nanogels showed excellent stimulus-response to glucose concentration.     

Cu(NH3)2(FOX-7)2的晶体结构和热行为

用l,1-二氨基-2,2-二硝基乙烯的钾盐[K(FOX-7)·H2O]和硝酸铜在氨水体系中合成了Cu( NH3)2(FOX-7)2,并培养得到了单晶.该晶体为单斜晶系,空间群P21/c,a=0.68818(7)nm,b=O.73083 (8) nm,c=1.319 66(14)nm,β=95.986°,V=0.6600...     

2,6-二乙酰基吡啶缩合苯磺酰肼铕配合物的合成及性质研究

合成了2,6-二乙酰基吡啶-苯磺酰肼Schiff碱(DAPBSH)及其与稀土Eu3+的配合物,采用元素分析、红外、核磁等表征手段确定了配体的结构,采用元素分析及热分析初步确定了配合物的结构Eu(DAPBSH)2(NO3)3·2H2O并对配合物的紫外、荧光性质做了初步研究。