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1.
A new [Ca(H2O)6]2+ cations-templated coordination polymer, namely {[Ca(H2O)6][Cu4(btec)2(μ3-OH)2]}n ( 1 , H4btec=1,2,4,5-benzenetetracarboxylic acid), has been prepared via the solvothermal reactions of CuCl2 ? 2H2O, CaCl2, and H4btec. X-ray structural analysis revealed that it features a tetranuclear [Cu4(COO)6(μ3-OH)2] cluster-based 3D anionic framework with (4,8)-connected scu topology that was further balanced by the isolated [Ca(H2O)6]2+ cations. The framework of 1 shows high thermostability under air atmosphere. Moreover, such compound shows high photocatalytic activity for the degradation of methyl blue (MB) with the degradation efficiency of 94.5 %, and the possible photocatalytic mechanism was also clarified.  相似文献   

2.
Reactions of metal acetates with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) and co-ligands gave rise to four new complexes, namely [Zn2(3-abpt)(beta)(DMF) (H2O)2]n·nH2O (1), [Zn(3-abpt)(ip)]n·3nH2O (2), [Zn(3-abpt)(ip)(H2O)2]n·2nH2O (3), and [Cu2(3-abpt)2(C6H5COO)4(H2O)2]n·2nH2O (4) (ip = isophthalate, beta = 1,2,4,5-benzenetetracarboxylate). Compound 1 is a 3D coordination polymer with uncommon 3,4-connected (62.8)2(62.82.102) network. Compounds 24 are all 1D coordination polymers, which exhibit diversity structures. Compound 2 is a tubular-like chain, 3 is a ring-like network, and 4 is a zigzag chain. Their thermal stabilities and the photoluminescence of 1 have also been investigated.  相似文献   

3.
The zinc(II) coordination polymer [Zn3(BPT)22‐H2O)2(H2O)2]n · n(DMA) ( 1 ) (H3BPT = biphenyl‐3,4′,5‐tricarboxylic acid, DMA = N,N′‐dimethylactamide) was obtained by the solvothermal reaction of H3BPT with Zn(NO3)2 in DMA/H2O mixed solvent. Single crystal X‐ray analysis reveals that compound 1 has a complicated 3D framework containing linear trinuclear [Zn3(COO)42‐H2O)2] clusters as building subunits, which can be simplified into a (3,6)‐connected rtl topological network with the Schläfli symbol {4.62}2{42.610.83}. The calculated results of total and partial density of states (DOS) indicate that the luminescence of 1 mainly originates from intraligand charge transfer.  相似文献   

4.
Complexes of ZnII salts with 4,4′-bipyridine-N,N′-dioxide (bpdo) have been prepared by solvathermal and solvent layering methods. Three complexes were obtained from ZnBr2: 1 is a 2D coordination polymer [Zn2Br4(bpdo)2]n, (2) a discrete trimetallic molecule [Zn3Br6(H2O)2(bpdo)4] and 3 a salt [ZnBr4][Zn(H2O)5(bpdo)]. Complexes 2 and 3 contain ZnII ions in both octahedral and tetrahedral coordination geometry. While in 2, these are covalently linked by bridging bpdo ligands forming zwitterionic trimetallic molecules, in 3 there is complete charge separation into [ZnBr4]2− anions and [Zn(H2O)5(bpdo)]2+ cations. When Zn(NCS)2 is used as starting material, a 1D coordination polymer [Zn(H2O)2 (bpdo)(NCS)2]n is obtained.  相似文献   

5.
Using Cu(II), Mn(II) or Co(II) salt and the flexible ligands, N-[(4-carboxyphenyl)-sulfonyl]glycine (H3L1) and N-[(3-carboxyphenyl)-sulfonyl]glycine (H3L2), a series of new coordination polymers, [Mn(phen)(H2O)4][HL1] (1), [Co3(L1)2(bipy)3(H2O)6]n·8nH2O (2), [Cu4(L1)2(OH)2(bipy)4]n·12nH2O (3), [Na(H2L1)(H2O)]n (4), [Mn2(HL2)2(dpe)3(H2O)2]n·ndpe (5), (phen = 1,10-phenanthroline, bipy = 4,4′-bipyridine, dpe = 1,2-di(4-pyridyl)ethylene), varying from 0D to 3D, have been synthesized and structurally characterized. Compound 1 has a [Mn(phen)(H2O)4]2+ cation and a HL12− anion. Compound 2 features a new 1D triple chain, based on octahedral cobalt atoms bridged by bipy molecules and terminally coordinated by two H3L1 ligands. Compound 3 has a 2D layered structure, constructed from new alternating chains where H3L1, hydroxyl and water molecules simultaneously act as bridging ligands. Compound 4 possesses a bilayer structure in which two adjacent layers are pillared by H3L1 ligands into a 2D bilayer network. Compound 5 is a unique 3D coordination polymer in which each Mn center binds two trans-located dpe molecules. The thermal stability as well as magnetic properties of 5 was also studied. This work and our previous work indicate that the positional isomer of the anionic N-[(carboxyphenyl)-sulfonyl]glycine is important in the construction of these network structures, which are also significantly regulated by the metal centers.  相似文献   

6.
Four new heterometallic polymers, [NiCd(mal)2(H2O)2]n·2nH2O 1, [NiZn2(Hcit)2(H2O)2]n 2, [CoCd2(Hcit)2(H2O)2]n 3, [CoZn2(Hcit)2(H2O)2]n 4 (H2mal=malonic acid, H4cit=citric acid) were synthesized and characterized. The photoelectric properties of the polymers were discussed by the surface photovoltage spectroscopy (SPS). The structural analyses indicate 1 is a Ni-Cd heterometallic polymer with 3D structure bridged by the mal2- group. 2-4 are all heterometallic polymers with 2D structures bridged by the Hcit3- group. The results of SPS for the four polymers reveal that there are wide photovoltage response bands in the range of 300-800 nm, which indicates that they all possess photoelectric conversion properties. By the introduction of the other metals, the SPS of heterometallic polymers are broadened obviously than the SPS of monometallic complexes. Moreover, the relationships between SPS and UV-Vis absorption spectra have been discussed.  相似文献   

7.
Two novel metal–organic coordination complexes [Cu(HBTC)(BPO)]·H2O (1) and [Co3(BTC)2(BPO)3(H2O)2]·5.25H2O (2), have been synthesized from hydrothermal reaction of metal chloride with the mixed ligands 1,3,5-benzenetricarboxylate (H3BTC) and bent dipyridyl based ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (BPO), and structurally characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction analysis. The results reveal that each dinuclear CuII unit is bridged by two kinds of different ligands (H3BTC and BPO) to form one-dimensional (1-D) chain structure in complex 1. The adjacent chains for 1 are further linked by π–π stacking interactions and hydrogen bonding interactions to form a three-dimensional (3-D) supramolecular framework. Complex 2 possesses a 3-D network composed of three different cobalt(II) centers [carboxylate-bridged dinuclear cobalt units and mononuclear cobalt ion] and bridging ligands BTC and BPO, which presents the first example of 3-D coordination polymer constructed from the BPO ligands simultaneously showing three different coordination modes. Moreover, the electrochemical behaviors of the two complexes bulk-modified carbon paste electrodes (1-CPE and 2-CPE) have been reported.  相似文献   

8.
Two novel inorganic-organic 3D network, namely{[Ln(L)1.5(H2O)2]·5H2O}n [Ln=Y (1), Ce (2)] [Ln(L)1.5(H2O)2]·5H2O [Ln=Y (1), Ce (2)], have been prepared through the assembly of the ligand 1,2-bis[3-(1,2,4-triazolyl)-4-amino-5-carboxylmethylthio]ethane (H2L) and lanthanide (III) salts under hydrothermal condition and structurally characterized by single-crystal X-ray diffractions. In complexes 1 and 2, the L2− anions adopt three different coordination fashions (bidentate chelate, bidentate bridging and bidentate chelate bridging) connecting Ln(III) ions via the oxygen atoms from carboxylate moieties. Both 1 and 2 exhibit 3D network structures with 2-fold interpenetration. Interestingly, the reversible desorption-adsorption behavior of lattice water is significantly observed in the two compounds. The result shows their potential application as late-model water absorbent in the field of adsorption material.  相似文献   

9.
In this study, we present eight new complexes and self-assemblies of Tb(III), Eu(III), Zn(II) and Cu(II) ions with novel pyridine carboxamides, L1 [methyl 4-methyl-3-(pyridine-4-carbonylamino)benzoate] and L2 [methyl 2-methyl-3-(pyridine-4-carbonylamino)benzoate], as heterocyclic ligands. Two luminescent and spatially organized coordination compounds were obtained with the use of the solvothermal synthesis method, (1) [Tb3(L1)4(BTC)3(H2O)3] (where BTC is benzene-1,3,5-tricarboxylic acid) and (5) [Eu(L2a)3(H2O)3](H2O)4. As a result of one pot reaction synthesis under reflux the d-electron metal ions and self-organization of ligands gave complexes (2) [Zn(L1)2Cl2], (3) [Cu(L1)2(SCN)2(H2O)], (4) [Cu(L1)2Cl2], hybrid salt (6) [(CuCl4)2-(L2b)22+](H2O), (7) [Cu(L2)2Cl2] and 1D-chain coordination polymer (8) [Cu(L2)2(SCN)2]. Identification of the obtained compounds was performed on the basis of the excitation, emission, 1H NMR, FT-IR spectra, luminescence lifetimes, SEM images, PXRD, single-crystal X-ray diffraction, MS, TGA and elemental analysis. Selected compounds were also analyzed in terms of their potential magnetic properties.  相似文献   

10.
Four new coordination compounds, [Zn(dba)(bpy)]n (1), {[Zn(dba)(phen)]·2H2O}n (2), [Cd(dba)(bpy)(H2O)2] (3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been prepared via solvothermal method and characterized by sin-gle-crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction. 1 and 2 possess 1D infinite chain structures. Complex 3 exhibits a mononuclear structure. Complex 4 owns bi...  相似文献   

11.
Two 2D coordiantion polymers, [Sr(p-ClPhHIDC)(H2O)]n (p-ClPhH3IDC = 2-(4-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (1) and [Cd3(p-ClPhH2IDC)2(p-ClPhHIDC)2(H2O)2]n (2) and one 3D polymer {[Co3(p-ClPhHIDC)3(H2O)3]·6H2O}n (3) have been prepared successfully under solvothermal conditions and structurally characterised by elemental analyses, IR and XRPD determinations, and have been further analysed by single-crystal X-ray diffraction. Polymer 1 exhibits a graceful 2D grid sheet structure. Polymer 2 can be regarded as a (3,3,4)-coordinated 2D network. Polymer 3 exhibits a 3D motif with 1D open channels and [Co12(p-ClPhHIDC)9] bihexagonal rings. The coordination features of the newly prepared imidazole dicarboxylate ligand, p-ClPhH3IDC, have been discussed from both theoretical and experimental aspects. Furthermore, the solid-state photoluminescence and thermal properties of the polymers have also been investigated.  相似文献   

12.
A bioinorganic approach into the problem of the isomorphous substitution of calcium(II) by lanthanide(III) ions in biological systems is discussed. Reactions of malonamic acid (H2malm) with CaII and NdIII sources under similar conditions yielded the compounds [Ca(Hmalm)2]n (1), [Nd(Hmalm)2(H2O)2]n(NO3)n (2) and [Nd(Hmalm)2(H2O)2]nCln·2nH2O (3·2nH2O). Their X-ray crystal structure data show that the malonamate(-1) ligand presents two different ligation modes and coordinates through the two carboxylate and the amide-O atoms, thus bridging three CaII ions in 1 and two NdIII ions in 2 and 3·2nH2O. Complex 1 is a 3D coordination polymer based on neutral repeating units, whereas 2 and 3·2nH2O are 1D coordination polymers based on the same cationic repeating unit. Hydrogen bonding interactions further stabilize the 3D framework structure of 1 and assemble the 1D chains of 2 and 3·2nH2O into 3D networks. The three complexes were characterized spectroscopically (IR, far-IR, and Raman) and the thermal decomposition of 2 and 3·2nH2O was monitored by TG/DTA and TG/DTG measurements. Variable-temperature magnetic susceptibility data for 2 are also reported. The bioinorganic chemistry relevance of our results is discussed.  相似文献   

13.
Reactions of N,N-diisopropylisonicotinamide (L) with anhydrous CuCl2, CuBr2 and Cu(ClO4)2·6H2O yielded: (a) an ionic product with the molecular composition of [CuL2(H2O)4]·2[CuLCl3] 1; (b) a coordination polymer [CuL2Br2]n2 and (c) a mononuclear complex [CuL4(C3H8O)2]·(ClO4)2] 3, respectively. Similarly, the reaction of N,N-diisobutylisonicotinamide (L′) with Cu(NO3)2·3H2O yielded a coordination polymer [{CuL′2(H2O)2}(NO3)2]n4. The ligands L and L′ coordinate in a monodentate fashion through the pyridine nitrogen atom to the metal centers in complexes 1 and 3. However, complexes 2 and 4 are coordination polymers in which the corresponding ligands (L and L′) act as bridging bidentate between metal centers to form 1D double chains. All the four complexes form networks through coordination polymerization and/or hydrogen bonding.  相似文献   

14.
Reactions of Cd(NO3)2 · 4H2O with 2‐quinolinecarboxylic acid (H‐QLC) in the presence of 1,4‐benzenedicarboxylic acid (H2‐BDC) or 1,3,5‐benzenetricarboxylic acid (H‐BTC) in DMF/H2O solvent afforded two compounds, namely, [Cd(QLC)(BDC)1/2(H2O)]n ( 1 ) and [Cd(QLC)(BTC)1/3]n ( 2 ). Both compounds are two‐dimensional (2D) frameworks but feature different cadmium‐carboxylate clusters as a result of the presence of the polycarboxylate ligands with different geometries and coordination preference. The dinuclear Cd2(QLC)2 units in 1 are bridged by the pairs of bridging water ligands to give a one‐dimensional (1D) chain, which is further linked by the second ligand of BDC2– to form a 2D structure. Compound 2 is constructed from unique hexanuclear macrometallacyclic Cd6(QLC)6 clusters, which are linked by the surrounding BTC3– ligands to generate a 2D structure. Photoluminescence studies showed both compounds exhibit ligand‐centered luminescent emissions with emission maxima at 405 and 401 nm, respectively.  相似文献   

15.
Two new 3D heterometallic frameworks, [Me2NH2][CaCd2(BTC)(HBTC)2] · 4H2O ( 1 ) and [Ba11Co2(BTC)83‐OH)22‐H2O)6(H2O)16] ( 2 ) (H3BTC = 1,3,5‐benzenetricarboxylic acid, Me2NH2 = protonated dimethylamine), were synthesized using solvothermal and hydrothermal techniques, respectively. Complex 1 features a 3D microporous framework; it contains hourglass‐like trinuclear [CaCd2(COO)6] clusters that are bridged by –COO groups and form zigzag chains. These chains are further interlinked by the –COO groups of BTC3– ligands into 2D layers with interesting flower‐like configuration, which, in turn, are connected by HBTC2– ligands to afford the 3D structure. Me2NH2+ cations not only balance the negative charges of the host framework but also play template roles to fill in the channels, further consolidating the whole framework. The complicated 3D network of complex 2 is constructed by the interconnection of 2D layers, which, in turn, are made of the infinite inorganic chains based on hexanuclear [Ba6] clusters, and these 1D chains are decorated by {CoO6} octahedrons. Interestingly, the 2D layer can be viewed as a unique structure composed of two different kinds of heart‐shaped rings, which partially overlapped in apical positions to produce a ten‐membered ring window. Moreover, the luminescence properties of 1 – 2 and the gas adsorption property of 1 have also been studied.  相似文献   

16.
This article presents the structure of a tight stacking coordination polymer, {Mn4(bpy)2(H2O)2(HBT C)4}n, 1, (bpy=4,4′-dipyridine, H3BTC=1,3,5-benzenetricarboxylic acid), which is self-assembled from the combination of MnCl2, H3BTC and bpy ligands via hydrothermal synthesis, and which has been further characterized by IR, element analysis, TG-DTA, variable-temperature magnetic susceptibility measurements. The overall structure of polymer 1 is the 3D interdigitating arrangement, constructed from the eight-connected Mn4 tetramer. Further, the magnetic measurements reveal that polymer 1 displays a weak antiferromagnetic behavior with θ?=??3.36?K between Mn(II) ions in the electronic configuration of d5 high spin (S?=?5/2).  相似文献   

17.
《Solid State Sciences》2012,14(3):317-323
Three transition metal coordination polymers [Zn2(H2L)(2,2′-bpy)2(H2O)]n∙2nH2O (1), [Zn2(H2L)(2,2′-bpy)2]n (2), and [Cd2(H2L)(2,2′- bpy)2(H2O)2]n∙2nH2O (3), have been assembled from a semirigid triangular multicarboxylate ligand 3,3′,3″-(1,3,5-phenylenetri(oxy))triphthalic acid (H6L) with the help of 2,2′-bipyridine (2,2′-bpy) ligand. X-ray single crystal diffraction analysis reveals that complex 1 crystallizes in the space group of Pī and displays a one-dimensional (1D) ladder chain structure constructed from 2,2′-bpy ligand and H2L ligand, which stacks together in an -ABCABC- motif, featuring a mutually embedded chained structure. In complex 2, the H2L ligands bridge the adjacent Zn(II) atoms into a complicated ribbon chain along the b axis. There is π–π stacking interaction between the chains, which results in the formation of a 2D supramolecular structure. Complex 3 also exhibits a 1D ladder-like chain. The different molecular structures for complexes 1 and 2 formed from the same H6L and Zn(NO3)2∙6H2O in different metal-to-ligand ratios in the presence of NaOH, reveals the influence of metal–ligand ratio on the structure of the coordination polymer. In contrast, a series of same reaction using Cd(NO3)2∙4H2O as a starting material instead of Zn(NO3)2∙6H2O only led to the formation of 3, illustrating the fact organic ligands display different coordination preferences at different metal ions. In addition, the thermal and luminescent properties of complexes 13 were also investigated.  相似文献   

18.
A series of transition metal coordination complexes, {[Cu(3‐Sptta)2] · 1/2H2O}n ( 1 ), {[Cd(3‐Sptta)2] · 1/2H2O}n ( 2 ), [Zn(3‐Sptta)2(H2O)4] ( 3 ), and [Co(3‐Sptta)2(H2O)4] ( 4 ) were synthesized under solvothermal and solvent evaporation conditions using the newly designed heterocyclic N/NS carboxylate ligand [2‐(3‐pyridyl)‐1,3,4‐thiadiazole‐5‐]‐thio‐acetate (3‐Sptta) as a main building block. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses and IR spectroscopy. The four complexes exhibit structural diversity: complexes 1 and 2 exhibit similar 2D “wave‐like” double‐layer framework with two shares of mutually parallel left‐handed and right‐handed helical chains, whereas 3 and 4 present mononuclear structures. Moreover, the thermal stabilities of complexes 1 – 4 were investigated. The luminescent properties of complexes 2 , 3 and the free ligand were also studied.  相似文献   

19.
Five mixed ligands coordination polymers [Ag4(apym)2(pma)·(H2O)2]n (1), {[Ag4(dmapym)4(pma)·(H2O)2]·(H2O)6}n (2), [Ag2(apyz)2(H2pma)·(H2O)4]n (3), {[Ag4(apyz)2(pma)·(H2O)2]·(H2O)2}n (4) and [Ag4(NH3)8(pma)·(H2O)6]n (5) (apym = 2-aminopyrimidine, dmapym = 4, 6-dimethyl-2-aminopyrimidine, apyz = 2-aminopyrazine, H4pma = pyromellitic acid) were synthesized and characterized. For 1 and 2, as the substituents change from H to methyl, the dimensions of 12 decrease from three-dimension (3D) to one-dimension (1D) due to the steric effect of methyl groups. For 3 and 4, as the ratios of Ag2O/apyz/pma vary from 1:1:1 to 2:1:1, the structure of 3 is a 1D ladder structure built from Ag-apyz double chains and pma anions, while the structure of 4 is a two-dimension (2D) grid. As excess ammonia is added to above four reaction systems, the structure of 5 contains unprecedented {[Ag(NH3)2]+}n chains and pma anions. The substituent on the pyrimidyl ring, ratios of reactants, solvent systems and ligand isomers intensively influence the coordination environments of metal ion and the coordination modes of the carboxyl group, and thus determine the structures of the coordination polymers. The photoluminescent properties of 15 were also investigated.  相似文献   

20.
Reactions of 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H3PyIDC) with a series of Ln(III) ions affords ten coordination polymers, namely, {[Ln(H2PyIDC)(HPyIDC)(H2O)2]·H2O}n [Ln=Nd (1), Sm (2), Eu (3) and Gd (4)], {[Ln(HPyIDC)(H2O)3]·(H2PyIDC)·H2O}n [Ln=Gd (5), Tb (6), Dy (7), Ho (8) and Er (9)], and {[Y2(HPyIDC)2(H2O)5]·(bpy)·(NO3)2·3H2O}n (10) (bpy=4,4′-bipyridine). They exhibit three types of networks: complexes 1-4 are isomorphous coordination networks containing neutral 2D metal-organic layers, while complexes 5-9 are isomorphous, which consist of cationic metal-organic layers and anionic organic layers, and complex 10 is a 2D network built up from 4-connected HPyIDC2− anion and 4-connected Y(III) ions. In addition, thermogravimetric analyses and solid-state luminescent properties of the selected complexes are investigated. They exhibit intense, characteristic emissions in the visible region at room temperature.  相似文献   

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