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1.
Three Cd(Ⅱ) metal-organic complexes, namely[Cd(phen)2Cl2](1),[Cd(phen)Cl2](2) and[Cd(phen)(cam)]·H2O(3)(phen=1,10-phenanthroline, H2cam=camphoric acid), were hydrothermally synthesized using Cd2+, phen and H2cam as raw materials under different conditions of pH values, reaction temperatures or reactant ratios. The prepared complexes were structurally characterized by means of single-crystal X-ray diffraction, and the results show that complex 1 is a 2D supramolecular complex, which consists of[Cd(phen)2Cl2] mononuclear subunits, while complex 2 shows a 1D chain structure, in which Cd(Ⅱ) ions are connected by chloride(Cl-) bridges, with phen hanging on both sides of the chain. No cam anions have been observed in the structures of complexes 1 and 2. In complex 3, cam connects Cd(Ⅱ) ions to construct a 2D network, in which phen acts as terminal ligands. The adjacent 1D chains for complex 2 and the adjacent 2D layers for complex 3 are further linked by hydrogen bonding interactions or π-π intermolecular interactions to form 3D supramolecular networks, respectively. The effects of reaction conditions on the assembly and structures of the complexes have been discussed. The fluorescent and photocatalytic properties of complexes 1-3 and the fluorescent sensing behaviors of complexes 2 and 3 have also been investigated.  相似文献   

2.
以N,N'-二(3-吡啶基)-吡啶-3,5-二甲酰胺(bppdca)和2-巯乙酸基烟酸(L)为混合配体,利用水热合成方法获得了一个二维的Co(Ⅱ)配位聚合物:{[Co(bppdca)(L)]·3H2O}n,并通过元素分析、IR和单晶X射线衍射等技术手段确定了其结构。该配合物分子式为C25H24N6O9SCo,单斜晶系,P21/c空间群,a=1.07419(9) nm,b=0.86166(6) nm,c=2.9853(2) nm,β=96.772(1)°,Z=4,V=2.743 9(4) nm3,Mr=643.49,Dc=1.558 g/cm3,F(000)=1324,μ=0.766 mm-1,S=1.051,R=0.0406,wR=0.1160。 晶体结构分析表明,配合物中的CoⅡ与来自2个bppdca配体的2个N原子、1个L阴离子的单齿羧基O原子和S原子以及来自另一个L阴离子的一个羧基中的2个O原子配位形成八面体配位构型。 相邻的Co通过L阴离子连接成一维螺旋链[Co(L)]n,相邻的左、右螺旋链通过成对的bppdca配体拓展成二维配位网络。 最终,相互平行的二维网络通过氢键作用拓展成三维超分子框架。 另外,还研究了该化合物的热稳定性、电化学性质、荧光性质以及选择性光催化性质。CCDC: 1010786  相似文献   

3.
A new 1D chain coordination polymer [Cd(dpq)(ox)0.5Cl]n(1) (dpq=dipyrido[3,2-d:2′,3′-f]quinoxaline and ox=oxalate) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and single crystal X-ray diffraction analysis. Compound 1 (CdClC15H8N4O2): monoclinic, space group P21/c, a=0.854 04(5) nm, b=2.094 90(13) nm, c=0.839 22(5) nm, Z=4, V=1.438(15) nm3, Mr=424.11, Dc=1.959 g·cm-3, F(000)=828.0, μ=1.719 mm-1, S=1.028, the final R=0.025 8 and wR=0.057 5. The crystal structure analysis indicates that the cadmium ion is coordinated by two oxygen atoms from a oxalate, two chelating nitrogen atoms from a dpq molecule and two Cl- anions. The adjacent Cd(Ⅱ) ions are linked by Cl- anions and oxalate ligands in alternate sequence to form a 1D chain coordination polymer and the adjacent chains are further connected by π-π stacking interactions to form a 2D supramolecular network. Moreover, the title compound exhibits blue emission in the solid state at room temperature. CCDC: 680748.  相似文献   

4.
Based on a new biscarboxyl-functionalized Schiff base ligand 1,2-cyclohexanediamino-N,N'-bis[3-methoxyl-5-(p-carboxyl-phenylazo)] salicylidene(H4L), four polymers,[(CH3)2NH2]2·[Mn3(L)2(H2O)4]·2DMF(CP1),[Fe2(L)(H2O)(DMF)](CP2),[(CH3)2NH2]·[Cu(HL)]·H2O(CP3) and[Ni2(L)(teta)]·2DMF·H2O(CP4), have been synthesized(teta=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). In CP1, both of the internal[N2O2] pocket and the external carboxylate groups of L4- anion are ligated by Mn2+ ions, and the structure displays a layer. In CP2, the Fe2+ cations are linked by L4- anions to form a binuclear double chain. CP3 displays a[Cu2(HL)2] dimer. In CP4, the Ni2+ ions are connected by L4- anions to form a chain. The structures are further linked by hydrogen bonds to form 2D or 3D supramolecular architectures, respectively. CP1 exhibits adsorption ability to three organic dyes.  相似文献   

5.
Cobalt(II) and copper(II) complexes with 1-allyl-2-methylimidazole (L), of general formula [ML2(NO3)2], have been prepared in the solid state. The compounds were characterised by structural, spectroscopic and magnetic measurements. The metal ions in both six coordinate complexes are surrounded by two nitrogen atoms of the imidazole rings and four oxygen atoms of the chelating nitrato group (the CoN2O4 and CuN2O4 chromophores). The structure of both chromophores is described by a very distorted tetragonal bipyramid. The formation of successive complexes of the azole with Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ in aqueous solution was followed potentiometrically. An irregularity in the Kn constants of successive Co2+ and Zn2+ complexes suggests a change in the coordination sphere of the central ions from octahedral to tetrahedral. With the Co2+–1-allyl-2-methylimidazole system, the change has been proven by inspection of the visible absorption spectra.  相似文献   

6.
研究了Keggin结构钼磷杂多化合物Na5[PM(H2O)Mo11O39]·nH2O(M=Mn2+,Co2+,Ni2+,Cu2+,Zn2+在溶液中的氧化还原性质,发现环境的改变可对杂多阴离子的极谱半波电位产生影响,其影响程度的大小决定于过渡金属离子本身的性质。取代后的钼磷杂多阴离子的半波电位顺序为Ni2+>Co2+>Zn2+>Cu2+>Mn2+,pH值的变化影响氧化还原性质,并阐述了变价金属Cu2+对杂多阴离子氧化还原性质的影响.  相似文献   

7.
The two ion-pair complexes, [pyH]2[Zn(mnt)2] (1) and [4,4′-bipyH2]-[Zn(mnt)2] (2), were synthesized, where mnt2− denotes maleonitriledithiolate, and [pyH]+, [4,4′-bipyH2]2+ represent pyridinium and diprotonated 4,4′-bipyridinium, respectively. Their single crystal structures show that there are strong bifurcated H-bonding interactions between the cations of the pyridinium derivative and the [Zn(mnt)2]2− anions in both 1 and 2. The bifurcated H-bonding interactions between the N–H of the pyridiniums and the CN groups of the mnt2− ligands give rise to a 2D layered H-bonding network, the adjacent layers come together in such way as mutual embrace to give a tight pack, thus 2D hydrogen-bonding sheets further develop into 3D H-bonding networks through weak C–HS and ππ stacking interactions in 1. As for 2, the cations and anions connect into several types of H-bonding macrorings ([2+2], [3+3] and [4+4]), these H-bonding macrorings fuse to extend into 2D layered structure, the interpenetration between [3+3] and [4+4] type H-bonding macrorings in the adjacent layers give further rise to novel 3D extended H-bonding networks, in which there are clearly parallel stacks of cations and the chelate rings of anions.  相似文献   

8.
Two new polyoxometalate(POM)-based hybrid compounds, [Cu(en)][H4Mo4O16]0.5(1)(en=ethylene- diamine) and [Ag(3-C5H6N2)2][H2PMo12O40](2)(3-C5H6N2=3-aminopyridine), containing different transition metal-amine subunits were hydrothermally synthesized and characterized by elemental analyses, infrared spectroscopy and single-crystal X-ray diffraction. For compound 1, each [H4Mo4O16]4-(Mo4O16) cluster was linked to four neighboring Mo4O16 clusters through four [Cu(en)]2+ subunits to yield a (2,4)-connected 2D layer, which was further extended to a 3D supramolecular network via hydrogen bonding interactions. For compound 2, the adjacent [H2PMo12O40]- clusters were bridged by [Ag(3-C5H6N2)2]+ subunits to generate a 1D chain. The electrochemical behaviors and the photocatalytic activities of compounds 1 and 2 were studied in detail.  相似文献   

9.
选择柔性的双吡啶双酰胺配体N,N'-双(3-吡啶甲酰胺基)-1,2-乙烷(3-bpye)、钼酸铵和氯化锌在水热条件下自组装制备了一个基于一维[H_2Mo_4O_(14)]_n~(2n-)链的三维锌配合物[Zn(3-bpye)(H_2Mo_4O_(14))(H_2O)_2],并通过元素分析、红外光谱、热重分析等技术手段研究了配合物的结构,并利用X射线单晶衍射分析进行了晶体结构表征。结构解析揭示标题配合物是三斜晶系,P-1空间群,晶胞参数a=0.61310(3)nm,b=1.04750(6)nm,c=1.06540(6)nm,α=78.5540(10)°,β=77.5350(10)°,γ=89.9050(10)°,V=0.65420(6)nm~3,M_r=981.47,D_c=2.491 g/cm~3,Z=1,F(000)=468,R_1=0.0290,ωR_2=0.1068。标题配合物中,金属锌离子连接一维[H_2Mo_4O_(14)]_n~(2n-)链形成一种二维无机双金属层[Zn(H_2Mo_4O_(14))]_n,相邻的层间又通过双齿配体3-bpye连接形成三维CdSO_4拓扑的骨架结构。配合物表现出强的荧光发射特性,而且其在紫外光照下对亚甲基蓝和罗丹明B均有明显的催化降解活性。  相似文献   

10.
Five transition metal coordination compounds, [Mn2(8-qoac)2(bdc)(H2O)4](1)(8-qoacH=quinoline-8-oxy- acetate acid, H2bdc=benzene-1,4-dicarboxylic acid), [Zn4(8-qoac)4(bdc)2]n(2), {[Cd2(8-qoac)2(Hip)2(H2O)2]· (H2O)4}n(3)(H2ip=benzene-1,3-dicarboxylic acid), [Pb3(8-qoac)2(bdc)1.5(H2O)Cl]n(4) and [Zn2(8-qoac)(8-ql)(bdc)]n (5)(8-Hql=8-hydroxyquinoline), were synthesized by hydrothermal syntheses of metal salts with benzenedicarboxy- lic acid and 8-qoacH. Compound 1 possesses a discrete dimer bridged by bdc2- ligand. Compound 2 presents a 2D layer network constructed from bdc2- linkers and 1D infinite ribbons, in which Zn(II) centers are bridged by 8-qoac- with a tetradentate binding mode. Compound 3 displays a 1D zigzag chain, with adjacent chains further connected via extensive O-H···O hydrogen bonds to generate a 3D supramolecular structure. Compound 4 shows a 3D framework containing trinuclear lead secondary building units and bdc2- linkers, in which a new coordination mode of 8-qoac- ligand is observed. In compound 5, Zn(II) ions are simultaneously bridged by 8-qoac-, 8-ql- and bdc2- ligands to form tetranuclear zinc units, which are further interlinked by bdc2- linkers to yield a 2D wave-like layer. Based on intraligand(IL)(π-π*) fluorescent emission, compounds 1―5 possess strong purple fluorescent emissions. In addition, the thermal stabilities of compounds 1―5 were studied.  相似文献   

11.
Three new gallium complexes formulated as [Ga(PDA)2][Ga(H2O)(PDA)(phen)]·4H2O(1), [Ga(PDA)2]· (H2IN)·2H2O(2) and [Ga(OH)(PDA)(H2O)]2(3)(H2PDA=pyridine-2,6-dicarboxylic acid; phen=1,10-phenanthroline; HIN=isonicotinic acid) have been synthesized under hydrothermal conditions. In the mixed-ligand system of complex 1, PDA2? and phen are connected to the central Ga3+ cation as tri- and bi-dentate ligands, respectively. In complex 2, each Ga3+ cation is six-coordinated by two PDA2? anions octahedrally. Complex 3 shows a binuclear structure, with the bond distance of Ga1-Ga2 being 0.30061(3) nm. The 3D supramolecular structures of the three complexes are constructed via hydrogen bonds and aromatic π-π packing interactions. All the three complexes exhibit intense blue emission at room temperature in the solid state, which are attributed to π*-π transition centered on the ligands.  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.
Single-phase Co-doped TiO2(CoxTi1-xO2) nanoparticles(NPs) synthesized via a simple sol-hydrothermal method were used as surface-enhanced Raman scattering(SERS) substrates. Interestingly, it was found that SERS signals were enhanced greatly compared to those of pure TiO2 nanoparticles when an amount of Co2+ ions were doped into the TiO2 lattice. Detailed results clearly show that Co element as Co2+ was incorporated into the TiO2 lattice and the defects were created due to the substitution of Co2+ ions for the Ti4+ ions. The Co2+ doping increases the defect concentration of CoxTi1-xO2 NPs. An amount of defects is beneficial to the charge-transfer so as to increase the SERS activities. A possible mechanism of charge-transfer from CoxTi1-xO2 NPs to molecules was then briefly discussed.  相似文献   

14.
Two 1D coordination polymers Cu2I(C6N3H4)2(1) and CuII(C6N3H4)2·H2O(2) based on benzotriazole(Bta) were hydrothermally synthesized by controlling the crystallization temperature. Single-crystal X-ray diffraction (XRD) analyses reveal that compound 1 is a 1D tubular structure constructed from two types of 1D chains {-Cu-N=N-N-}n, where the Cu(I) ions adopt linear, triangular, and tetrahedral coordination modes to connect two types of Bta ligands via π-π interaction inside the tubular-like chain. For compound 2, the Cu(II) ions assume a quadrilateral coordination mode linking to the Bta ligands to give 1D straight chains, which stacks through π-π interactions to construct a 2D layer structure. Further characterizations including elemental analyses, infrared IR spectra, thermogravimetric(TG) analyses and luminescence properties have been done.  相似文献   

15.
利用四[1-(1, 2, 4-三氮唑基)甲基]间苯二酚杯[4]芳烃配体(TTR4A)在溶剂热的条件下合成了两个配位聚合物,[[Zn2(TTR4A)(L)2]·DMF·4H2O]n(化合物1) (DMF = N, N-二甲基甲酰胺)和[[Co(TTR4A)Cl2]·DMA·H2O]n (化合物2) (H2L = 4, 4’-联苯二甲酸) (DMA = N, N-二甲基乙酰胺)。通过单晶X射线衍射方法对这两个配位聚合物的结构进行了确定。利用红外、元素分析、粉末X射线衍射(PXRD)和热重表征手段对化合物1和2进行了表征。在化合物1中,四个L配体连接着四个Zn(Ⅱ)离子形成了环状的Zn4L4结构单元,该结构单元进一步地被TTR4A链接形成了一维链状结构。在化合物2中,TTR4A的四个三氮唑基团各连接一个Co(Ⅱ)离子形成二维层状结构。此外,我们对化合物1的荧光性能进行了研究,荧光测定表明固态条件下化合物1发出很强的荧光,并能够选择性地对Fe3+、Cr2O72−和硝基苯分子产生响应。  相似文献   

16.
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   

17.
Four oxalate-bridged transition-metal supramolecular compounds [Co2(im)4(ox)2] 1, [Co(im)2(ox)] 2, [Mn(2,2′-bpy)(ox)] 3 and [Fe(H2O)2(ox)] 4 (im, imidazole; ox, oxalate; bpy, bipyridine) were obtained from the simple hydrothermal reactions of Mn+oxL (M, transition metal; L, aromatic N-donor ligand) system. They all exhibit the 1-D chain structures, consisting of the (or ML2+) units linked by oxalate bridges. Interestingly, the 1-D oxalate chains in the title compounds are further self-assembled into the 3-D supramolecular networks through the interchain various secondary bonding interactions. Because the units adopt the different configuration, the oxalate chains show either zigzag type as in compounds 1–3 or linear type as in compound 4. Compounds 1 and 2 are isomeric, and only in packing modes of interchain im molecules there exists the difference.  相似文献   

18.
常温反应条件下制备了4个基于乙二胺和1,5-萘二磺酸的配位化合物[M(en)(H_2O)_4]·1,5-nds·(H_2O)_2(M=Ni(1),Co(2),Cd(3),Cu(4),nds=1,5-萘二磺酸;en=乙二胺),并通过红外光谱、元素分析、X射线单晶衍射、X射线粉末衍射和热重分析等技术手段确定了其晶体结构。结构分析表明,该系列配合物属于同构体系,单斜晶系,C2/c空间群。以配合物1为例,其晶胞参数为a=1.69026(19)nm,b=1.01373(11)nm,c=1.3448(3)nm,α=90°,β=120.2650°,γ=90°,V=1.9901(5)nm~3,Z=4,Dc=1.713 g/cm~3,F(000)=1072,R_1=0.0326,wR_2=0.0867。该系列配合物的中心金属为六配位模式,与来自乙二胺的2个N原子和4个H_2O中的氧原子配位。游离水与磺酸氧和配位水之间存在着丰富的氢键作用,构筑成三维的网络结构。测定了以Cd为中心金属配合物3的荧光光谱,发现其在对于甲醇的小分子识别性能方面具有应用前景。  相似文献   

19.
A new nitronyl nitroxide NIT2-bithph (1) and its manganese(II) compound [Mn(hfac)2(IMHBithph)]2·(NIT2-bithph)(C6H14) (2) (hfac = hexafluoroacetylacetonate; NIT2-bithph = 4,4,5,5-tetramethyl-2-(bithiophenal-2-yl)imidazoline-1-oxyl-3-oxide; IMHBithph = 1-hydroxy-2-bithiophenal-4,4,5,5-tetramethyl-4,5-dihydro- 1H-imidazole) have been synthesized and structurally characterized by X-ray diffraction methods. The units of compound 1 were connected as one-dimensional chain by the intermolecular hydrogen bonds which afford an intermolecular antiferromagnetic interaction between nitronyl nitroxide radicals within the chain (J = −1.89 cm−1). Compound 2 resulting from the reaction of Mn(hfac)2·2H2O and NIT2-bithph is dinuclear and includes the reduced amidino-oxide form of NIT2-bithph, it is made up of three parts: a [Mn(hfac)2(IMHBithph)]2 dimer unit, an uncoordinated NIT2-bithph radical and a noncoordinated solvent molecule of hexane, the molecule of radical is hydrogen bonded to its reduced form. Two reduced IMHBithph ligands bridge the two manganese(II) ions through their amidino-oxide oxygen atoms resulting in a small intramolecular antiferromagnetic interaction between the manganese ions (J = −1.55 cm−1).  相似文献   

20.
本文设计了一个新型含苯-甲基-苯骨架的席夫碱配体,构筑了两个具有矩形结构的锌-稀土纳米簇[Ln2Zn2L2(OAc)6] (Ln = Yb (1)和Er (2))。该席夫碱配体以“伸展型”配位模式与稀土离子进行配位,使这些锌-稀土纳米簇表现出较大的分子尺寸结构(0.7 nm × 1.1 nm × 2.2 nm)。荧光性质研究表明,由Zn/L组成的发色基团能有效敏化1和2中Yb3+和Er3+离子的近红外发光。通过对荧光量子产率及寿命进行分析发现,Zn/L对Yb3+离子的传能效率要高于Er3+离子。  相似文献   

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