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1.
采用室温溶液挥发法合成了五种结构新颖的镧系配合物,其结构通式为[Ln(2,4-DFBA)3(phen)]2 (Ln=Sm 1, Eu2, Er 3, 2,4-DFBA为2,4二氟苯甲酸的简写,phen为1,10-菲啰啉的简写),[Ln(2-Cl-6-FBA)2(terpy)(NO3)(H2O)]2 (Ln=Tb4, Dy 5, 2-Cl-6-FBA为2-氯-6-氟苯甲酸的简写, terpy为2,2’:6’2’’-三联吡啶的简写)。五个配合物可以分为两个系列,使用不同的镧系离子作为中心离子。通过X射线单晶分析,5种配合物均属于单斜晶系,空间群为P21/n。配合物1,2和配合物3虽然具有相同的分子通式,但配位方式明显不同,形成了前者为9配位的松饼型,后者是8配位的双帽三棱柱几何构型。二维面状超分子结构的形成方式也明显不同,区别在于配合物1和2通过微弱的π-π堆积作用形成。配合物4和5是同构的,结构中引入了硝酸根离子较为有趣,通过C―H···F氢键和π-π堆积作...  相似文献   

2.
双钼配合物〔Mo(DTC)4〕〔MoCl6〕(其中DTC=S2CN(C2H5)2)由于它在一个分子中同时包含两个处于不同配位环境中的、表观氧化态都是正五价的钼,即:一个Mo5+与四个DTC配体构成配位阳离子〔Mo(DTC)4+;另一个Mo5+与氯离子配体构成配位阴离子〔MoCl6-而独具特色。本文首次发表了它的红外和紫外-可见吸收光谱数据,并通过初步的光谱分析,确定了上述配合物的结构特征。  相似文献   

3.
制备了以3-((4,6-二甲基-2-嘧啶基)硫代)-丙酸(HL)和菲咯啉(Phen)为配体的2个三元稀土配合物[Eu(L)3(Phen)]2·2H2O(1)和[Tb(L)3(Phen)]2·2H2O(2),并对其结构进行了表征。单晶X射线衍射分析表明它们是同构的。2个稀土离子(Ln)由4个羧酸配体桥接,形成二聚体排列。其余2个羧酸配体和Phen以双齿螯合方式与Ln配位。Ln的配位数为9,具有扭曲的单端方形反棱柱配位多面体构型。固态光致发光测试表明,这2种配合物都显示了金属中心的特征发射带。  相似文献   

4.
使用多齿席夫碱配体,通过溶剂热法,设计与合成了3例新的稀土配合物[Ln2(L)2(acac)2(CH3OH)2]·2CH3OH(Ln=Sm(1)、Gd(2)、Ho(3),H2L=吡啶?2?羧酸?(1?甲基?3?氧代丁烯基)?酰肼),并对配合物1~3的结构与磁性质进行了系统的研究。单晶结构测试结果表明配合物1~3为同构,每个中心稀土Ln(Ⅲ)离子为八配位,其配位几何构型为扭曲的四方反棱柱;相邻的中心稀土Ln??离子通过2个μ2?O连接形成了平行四边形的[Ln2O2]核心。磁性测试揭示配合物2具有磁制冷性质,其最大磁熵变(-ΔSmax)为31.9 J·K-1·kg-1(T=2.0 K,ΔH=70 kOe);配合物3表现出了慢磁驰豫行为。  相似文献   

5.
用常规溶液法由氯化锰(MnCl2·4H2O)和4-甲基-1,2,3-噻二唑-5-甲酸(HL)反应制备了配位聚合物[Mn3(L)6(H2O)4]n(1),加入配体菲咯啉(phen)后合成了配合物[Mn2(phen)4(H2O)2Cl2](L)2·3H2O (2)。用元素分析、红外光谱、热重分析及单晶X射线衍射进行了配合物的表征。单晶结构分析表明:配合物1属单斜晶系P21/c空间群,3个锰离子通过6个L-中的氧原子双齿桥联,形成了线型三核簇合物单元,簇合物单元间又通过其中一个噻二唑环上的氮原子与另一个簇合物单元的锰原子配位,形成层状结构;配合物2属三斜晶系■空间群,锰离子分别与1个氯离子、1个水分子和2个phen分子中的4个氮原子配位,形成六配...  相似文献   

6.
韩洋  杨维春  王科志 《化学学报》2007,65(21):2382-2386
合成并表征了一个新的Ru(II)配合物[Ru(bpy)2(hedppc)](ClO4)2 {bpy=2,2'-联吡啶, hedppc=二联吡啶[3,2-a: 2',3'-c]吩嗪-11-羧酸(2-羟乙基)酯}. 通过紫外-可见吸收光谱、与溴化乙锭竞争实验、粘度测量和DNA裂解实验研究了配合物与小牛胸腺DNA的相互作用性质. 结果表明配合物以插入模式与DNA键合,键合常数Kb=(6.99±1.34)×106 mol-1•L (s=2.03±0.04)与母体配合物[Ru(bpy)2 (dppz)]2+相近,但光致发光和溶剂变色等光学性质与[Ru(bpy)2 (dppz)]2+有明显的差别.  相似文献   

7.
在溶剂热条件下,以2-吡啶甲醛肟(HL)为主配体,Zn(OAc)2·2H2O和NiCl2·6H2O为金属盐,合成了一个Ni2Zn2簇配合物[Ni2Zn2(L)4Cl2(CH3O)2](1),通过元素分析、红外光谱、单晶X射线衍射等对其结构进行了表征。研究了该配合物的磁性及光催化降解染料的性能,结果表明:配合物1属于正交晶系,Pna21空间群,其分子中包含2个Ni离子,2个Zn离子,4个L-配体,2个Cl-离子和2个CH3O-离子。磁性研究表明Ni…Ni离子间存在弱的反铁磁相互作用。光催化降解染料的研...  相似文献   

8.
合成了一种新的氧化膦取代杯芳烃衍生物的稀土离子(La3+,Eu3+)硝酸盐配合物.通过元素分析和红外光谱对配合物进行了表征.在无水甲醇中培养出了配合物的单晶,用X射线单晶衍射法测定了其晶体结构.硝酸镧配合物晶体[L·La(OH2)(NO3)2]NO3{L为四(亚甲基二苯基氧化膦)杯[4]芳烃}属四方晶系,空间群P43212,晶胞参数a=b=1.8977(4)nm,c=3.1087(11)nm;Z=4;V=11.196(5)nm3;Dc=1.097g/cm3,F(000)=3712,μ=0.491mm-1,R1=0.1181,wR2=0.1930.硝酸铕配合物晶体[L·Eu(OH2)(NO3)2]NO3·CH3OH属单斜晶系,空间群C2/c,晶胞参数a=2.88172(11)nm,b=5.4015(2)nm,c=2.01189(7)nm;β=133.4067(9)°,Z=8;V=22.7511(14)nm3,Dc=1.106g/cm3,F(000)=7464,R1=0.0671,wR2=0.1794.2个配合物的晶体结构相类似,配合物中配体的4个磷氧键上的氧原子、2个双齿配位的硝酸根中的4个氧原子还有1个水分子中的氧原子分别参与了配位.中心离子配位数为9,配位多面体为单帽四方反棱柱体.另外在铕配合物的杯芳烃中还包合了1个甲醇分子.  相似文献   

9.
在酸性介质、含水溶剂中合成了四元混配化合物[Ln(BA)2(NO3)(phen)]2(BA=苯甲酸根;Ln=La,Ce,Pr,Nd,Sm,Eu,Dy,Gd,Tb,Er),用元素分析、IR、DTA-TG等方法对配合物进行了表征.研究了配合物的顺磁性能和荧光性能.镨配合物的单晶衍射结果表明,配合物属三斜晶系,双核,Pr3+的配位数为9,4个BA呈二种配位方式,丰富了四元配合物的结构表现形式.  相似文献   

10.
穆华荣  毕欣  孙晶  颜朝国 《应用化学》2016,33(2):206-212
通过带有不同长度的4-(4-氯烷氧基苯基)-2,2':6,2″-三联吡啶和N-甲基咪唑在甲苯中加热反应,制备了3种由烷氧基桥联的新型三联吡啶咪唑配体。研究了配体和过渡金属离子的配位反应。测定了三联吡啶咪唑铜配合物的单晶分子结构,在铜配合物中,Cu(Ⅱ)和两个三联吡啶单元形成扭曲八面体配位方式。Monoclinic,空间群P 21/c;a=1.7229(3) nm,b=1.5924(2) nm,c=2.1590(3) nm,α=90°,β=101.332(2)°,γ=90°,Mr=1298.09,V=5.8078(15) nm3,Dc=1.485 mg/m3,Z=4, F(000)=2684。  相似文献   

11.
以正十二烷作稀释剂, 研究了二(2-乙基己基)二硫代次膦酸(D2EHDTPA)对HNO3溶液中Am3+和Eu3+的萃取行为. 考察了酸度、 萃取剂及NO3-浓度和皂化度对萃取的影响. 在考察的pH范围(2.5~4.5)内, D2EHDTPA萃取Am3+和Eu3+的分配比(D)随pH值增大而增加; pH=3.65时, 分离因子(SFAm/Eu)值达到最大(4000). 随D2EHDTPA浓度的增加, DAmDEu值均增加. 斜率分析表明, D2EHDTPA萃取Am3+和Eu3+主要形成3:1和2:1型的萃合物. NO3-未直接参与D2EHDTPA对Am3+和Eu3+的萃取反应. D2EHDTPA经NaOH皂化后, 萃取能力显著增强, SFAm/Eu值提高到104量级, 萃取容量约为理论值的60%. 此外, 使用高分辨质谱、 红外光谱和等温微量热滴定方法研究了D2EHDTPA与Eu3+的配位化学行为, 得到了金属离子与配体的组成比、 络合物稳定常数以及配位热力学参数ΔH, ΔS和ΔG值.  相似文献   

12.
Six ternary lanthanide complexes formulated as [Ln(2, 4, 6-TMBA)3(5, 5'-DM-2, 2'-bipy)]2 (Ln = Pr 1, Nd 2, Sm 3, Eu 4, Gd 5, Dy 6; 2, 4, 6-TMBA = 2, 4, 6-trimethylbenzoate; 5, 5'-DM-2, 2'-bipy = 5, 5'-dimethyl-2, 2'-bipyridine) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, etc. The results of crystal diffraction analysis show that complexes 1–6 are binuclear units, crystallizing in the triclinic space group. Complexes 1–5 are isostructural, and each of the central metal ions has a coordination number of 9. The asymmetric unit of complexes 1–5 consists of one Ln3+, one 5, 5'-DM-2, 2'-bipy ligand, and three 2, 4, 6-TMBA- moieties with three coordination modes: chelation bidentate, bridging bidentate, and bridging tridentate. The coordination geometry of Ln3+ is distorted monocapped square antiprismatic. The binuclear units of complexes 1–5 form a one-dimensional (1D) supramolecular chain along the c-axis via ππ stacking interactions between the 2, 4, 6-trimethylbenzoic acid rings. The 1D chains are linked to form a supramolecular two-dimensional (2D) sheet in the bc plane via ππ stacking interactions between the pyridine rings. Although the molecular formulae of complex 6 and complexes 1–5 are similar, the coordination environment of the lanthanide ions is different in the two cases. The asymmetric unit of complex 6 contains a Dy3+ ion coordinated by a bidentate 5, 5'-DM-2, 2'-bipy and three 2, 4, 6-TMBA- ligands adopting bidentate and bridging bidentate coordination modes. The Dy3+ metal center has a coordination number of 8, with distorted square antiprismatic molecular geometry. The binuclear molecule of 6 is assembled into a six-nuclear unit by ππ weak staking interactions between two 5, 5'-DM-2, 2'-bipy ligands; then, adjacent six-nuclear units form a 1D chain via offset ππ interactions between 5, 5'-DM-2, 2'-bipy ligands on different adjacent units. The adjacent 1D chains are linked by C―H···O hydrogen bonding interactions to form a 2D supramolecular structure. The thermal stability and thermal decomposition mechanism of all the complexes are investigated by the combination of thermogravimetry and infrared spectroscopy (TG/FTIR) techniques under a simulated air atmosphere in the temperature range of 298–973 K at a heating rate of 10 K·min-1. Thermogravimetric studies show that this series of complexes have excellent thermal stability. During the thermal decomposition of the complex, the neutral ligand is lost first, followed by the acid ligand, and finally, the complex is decomposed into rare earth oxides. The three-dimensional infrared results are consistent with the thermogravimetric results. The photoluminescence spectra of complex 4 show the strong characteristic luminescence of Eu3+. The five typical emission peaks at 581, 591, 621, 651, and 701 nm correspond to the 5D07F0, 5D07F1, 5D07F2, 5D07F3, and 5D07F4 electronic transitions of Eu3+, respectively. The emission at 621 nm is due to the electric dipole transition 5D07F2, while that at 591 nm is assigned to the 5D07F1 the magnetic dipole transition. The lifetime (τ) of complex 4 is calculated as 1.15 ms based on the equation τ = (B1τ12 + B2τ22))/(B1τ1 + B2τ2), and the intrinsic quantum yield is calculated to be 45.1%. Further, the magnetic properties of complex 6 in the temperature range of 2–300 K are studied under an applied magnetic field of 1000 Oe.  相似文献   

13.
Herein, we reported the synthesis and investigation of highly luminescent quadruple-stranded helicate (C6H16N)4[Eu2(MBDA)4]2.3C4H10O·4C2H3N(1-Eu)[H2MBDA=N-methyl-4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl)di- phenylamine] for its stability toward metal ions in the solution. The material was characterized via X-ray crystallographic technique, Fourier transform infrared(FTIR) spectroscopy and electrospray ionization quadrupole time-of- flight(ESI-TOF) mass spectrometry. The results on the luminescence quantum yields clearly demonstrate that the ligand can effectively sensitize the luminescence of the Eu3+ ions(Φoverall=15%). Upon the addition of different metal ions(i. e., Ag+, Cd2+, Zn2+, Fe3+, Al3+ and Ni2+) to the CH3CN solution of compound 1-Eu, the emission intensities of Eu3+ ions at 612 nm were affected to some extent, which could be attributed to the presence of ion exchanges between Eu3+ ions and the metals ions, and the result was confirmed by ESI-TOF mass spectrometry.  相似文献   

14.
王琦  仝玉章  贾晓普  杨春  王庆伦  廖代正 《应用化学》2019,36(12):1397-1405
在水热条件下,基于配体N,N'-双(3-吡啶基)-对苯二甲酰胺(3-bptpa)和1,3,5-苯三甲酸(1,3,5-H3btc),合成了一例具有二维格子结构的钴(Ⅱ)MOF[Co(3-bptpa)(1,3,5-Hbtc)]·2H2O(1),并进行了红外光谱(FT-IR)、元素分析(EDS)、差热-热重分析(DTA-TG)、X射线单晶衍射(XRD)和磁学表征。 结果表明,每个1,3,5-Hbtc2-提供1个螯合配位羧基和1个桥连配位羧基与Co(Ⅱ)离子配位。 中心对称的二聚体[Co(3-bptpa)(1,3,5-Hbtc)]2通过桥连配位的羧基连接成1D梯形链,相邻的梯形链通过3-bptpa与Co(Ⅱ)的配位作用连接为2D格子,从而形成CoN2O4变形八面体的配位构型。对配合物1在16~300 K的磁化率数据,使用八面体场下旋轨耦合的各向同性的单离子近似和分子场理论进行分析,Co(Ⅱ)离子表现强的旋轨耦合作用(λ=-100.4 cm-1),相邻的Co(Ⅱ)离子之间通过桥连配位的羧基传递弱的反铁磁相互作用(zj'=-0.618 cm-1)。  相似文献   

15.
为了探究在Dy~(3+)掺杂Ba_3Y(PO_4)_3荧光粉中共掺Eu~(3+)离子对其发光性能的影响,我们采用传统高温固相法制备了一系列Dy~(3+)、Eu~(3+)单掺杂和共掺杂Ba_3Y(PO_4)_3荧光粉。通过X射线衍射(XRD)、荧光发射光谱和荧光衰减曲线对样品进行了表征。结果表明,所制备的荧光粉呈闪铋矿立方相。在近紫外光激发下,Ba_3Y(PO_4)_3∶Dy~(3+)发射光谱在487和578 nm处有两个窄带发射峰,呈冷白光发射;Ba_3Y(PO_4)_3∶Eu~(3+)发射光谱的窄带发射位于594和616 nm处,呈发橙红光。在Ba_3Y(PO_4)_3∶Dy~(3+),Eu~(3+)中,由于Eu~(3+)离子补偿Dy~(3+)冷白光发射所缺的红色组分,从而实现了色纯度高、色温适中的暖白光发射。进一步探索了Ba_3Y(PO_4)_3∶Dy~(3+),Eu~(3+)荧光粉发光机理。所制备的Ba_3Y(PO_4)_3∶Dy~(3+),Eu~(3+)单基质白光荧光粉在白光近紫外激发白光二极管(UVWLED)领域具有潜在应用价值。  相似文献   

16.
A new transition metal complex, [Cu(N-MeIm)4(BF4)2](N-MeIm=N-methylated imidazoles, BF4= tetrafluoroborate), was synthesized via the solvothermal method in ionic liquid. The ionic liquid acts as thermal decomposition reaction medium, soft temple agent and ligand compound. The central Cu(II) ion is coordinated by four N atoms from four N-methylated imidazole ligands, and the four N-methylated imidazole rings are perpendicular to each other. The crystal structure of [Cu(N-MeIm)4(BF4)2] was determined by single crystal X-ray diffraction. The results of thermogravimetry(TG) and Fourier transform infrared spectrometry(FTIR) analyses were in accordance with that of crystal structure. The complex showed strong ligand-based absorbance with maximum wavelength at 208 and 231 nm, which are attributed to π-π* transition of the N-methylated imidazole ligands.  相似文献   

17.
The X-ray crystal structure of an anionic octacoordinate Eu3+ complex of the formula K12H8[Eu4(EDTMP)4] · 45H2O, where EDTMP is the ethylenediaminetetra(methylenephosphonate) anion, hereinafter referred to as I, has been determined. The crystal consists of cyclic tetrameric complex anions, in which the surrounding of each Eu3+ ion is composed of two nitrogen atoms and six oxygen atoms from phosphonate groups. One of the phosphonate groups in the ligand molecule is tridentate (O:O′,O″), thus giving rise to the formation of the tetramers. The compound was characterized by UV–Vis electronic spectroscopy. At room and liquid nitrogen temperatures the complex shows luminescence from both 5D0 and 5D1 states, the latter one, which is very rare in Eu3+ compounds with organic ligands, is probably brought about by the saturation of the coordination sphere with the phosphonate groups.  相似文献   

18.
采用水热法合成了一个钨-钒簇聚物[Cu(en)2]2[V{Cu(en)2(H2O)}2]·3H2O(1, en=乙二胺), 并通过X射线单晶衍射、 元素分析、 傅里叶变换红外光谱、 X射线粉末衍射、 热重分析、 价键计算、 X射线光电子能谱、 电子顺磁共振和磁性分析对其结构和性能进行了表征. 结果表明, 化合物1是以双支撑的四帽Keggin结构 [(VO4){Cu(en)2(H2O)}2]4- 钨-钒簇合物阴离子为基本结构单元, 与4个[Cu(en)2]2+配合物阳离子以共价键和弱键相连接形成二维层状结构, 相邻层又通过氢键连接成三维超分子网络. 研究了化合物1的磁性及光催化降解罗丹明B的活性.  相似文献   

19.
Raman Batheja  Ajai K. Singh 《Polyhedron》1997,16(24):4337-4345
The nucleophile [ArTe] generated in situ borohydride solution of Ar2Te2, reacts with 2-(chloromethyl) tetrahydrofuran and 2-(2-bromoethyl)-1,3-dioxolane resulting in L1 and L2, respectively. The complexes of palladium(II) and platinum(II) with L1/L2 having stoichiometries [MCl2·L2], [ML2](ClO4)2, [(DPPE)ML2](ClO)4)2, [(PPh3)2ML2](ClO4)2 and [(phen)ML2](ClO4)2 (where L = L1/L2 DPPE = Ph2PC H2CH2PPh2, PHEN = 1,10-phenanthroline and M = Pd/Pt) have been synthesized. IR, 1H, 125Te{1H} and 31P{1H} NMR and UV-vis spectral data of these species in conjunction with their molar conductance and molecular weight data have been used to authenticate the new species. In all complexes (1–20) the ligands L1 and L2 are coordinated through tellurium and in the complexes of formula [ML2](ClO4)2 (M = Pd, Pt) the ligand is bidentate with the oxygen atom used in complexation. In solution, complexes PtCl2L2 exist as a mixture of cis and trans isomers whereas only the trans isomer was observed for the palladium analogues. The [(phen)PdL2](ClO4)2(Q) quenches 1O2 readily. The plot of log [Q] vs time is linear. Mechanism compatible with the experimental observations is proposed.  相似文献   

20.
Four europium trifluoroacetate complexes, Eu(CF3COO)3·bpy(bpy=2,2′-bipyridine)(1), Eu(CF3COO)3· phen(phen=1,10-phenanthroline)(2), Eu(CF3COO)3·2bp(bp=benzophenone)(3) and Eu(CF3COO)3·2tppo(tppo=triphenyl-phosphine oxide)(4) were synthesized and characterized by elemental analysis, Fourier transform infrared(FTIR) spectroscopy, photoluminescence(PL) spectroscopy and thermogravimetric analysis(TGA). The PL spectra of the complexes at room temperature show the strong typical Eu3+ ion red emission, due to the efficient energy “antenna absorption” of ligands and transitions of Eu3+ ion between 5D07FJ(J=0―4). The long lifetime and high quantum yield reflect that the multiphonon relaxations by coupling to O―H and C―H vibrations were reduced. According to the photoluminescent spectra, the Judd-Ofelt parameters Ω2 and Ω4 of the complexes were calculated and the radiative properties were also presented. The 5D0 radiative lifetime, quantum yield and the stimulated emission cross-section of the complexes are excellent, which prove that they have promising optical properties for liquid laser. The thermal analyses indicate that they are quite stable to heat.  相似文献   

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