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1.
Two new compounds, [Cd2(bptc)(bpimb)(H2O)]?·?2H2O (1) and [Cd2(bptc)(bpib)]?·?4H2O (2) (where H4bptc?=?biphenyl-3,3′,4,4′-tetracarboxylic acid, bpimb?=?1,3-bis((2-(pyridin-2-yl)-1H-imidazol-1-yl)methyl)benzene, bpib?=?1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane), were synthesized by reactions of the corresponding metal salts with H4bptc and N-containing auxiliary ligands and their structures have been determined by single-crystal X-ray diffraction. Compound 1 is built by Cd4-clusters which further construct a 3-D (3,8)-connected framework with tfz-d notation; 2, also built by Cd4-clusters, is a 3-D (4,8)-connected framework with (32?·?42?·?52)(34?·?48?·?512?·?64) topology. In addition, the elemental analyses, infrared spectra, fluorescence, and thermogravimetric analyses for 1 and 2 are discussed.  相似文献   

2.
Six transition metal coordination polymers based on a semirigid tetracarboxylic acid and the multidentate N-donor ligands have been synthesized by the hydrothermal method, namely, {[Co(H2obda) (μ2-H2O) (H2O)2]·2H2O}n (1), {[Co(obda)0.5(bpe) (H2O)2]·3H2O}n (2), {[Zn(H2obda) (H2O)4]·H4obda·6H2O}n (3), {[Zn(bpy) (H2O)4]·H2obda}n (4), {[Ni(bpy) (H2O)4]·H2obda}n (5) and {[Cu(H2obda) (bpy)2]}n (6) (H4obda = 1,4-bis(4-oxy-1,2-benzene dicarboxylic acid)benzene, bpe = 1,2-Bis(4-pyridyl)ethylene), bpy = 4,4′-bipyridine). Compounds 16 were structurally characterized by the elemental analyses, infrared spectra, and single crystal X-ray diffractions. Compounds 1–2 exhibit the 2D quadrilateral and polygonal layered grid structures, respectively; a 3D supramolecular structure of 2 has been build via π···π and hydrogen bonds interactions. Compounds 3–6 reveal the 1D zigzag and linear chains structures, respectively; furthermore, 3–5 display the diverse 3D supramolecular structures via hydrogen bonds, respectively. The 1-D infinite water chain in 3 has been found between the lattice water molecules. In addition, the thermogravimetric analyses of 16, magnetic property of 1, and photoluminescence of 34 have been investigated, respectively.  相似文献   

3.
Five cadmium(II) metal-organic frameworks, namely [Cd(BIPA)(daf)(H2O)3] · 2H2O (1), Cd2(BDC)2(pdon)2(H2O)2 (2), Cd(BIPA)(pdon) (3), Cd(BIPA)(daf) (4) and [Cd2(BIPA)2(pdon)2] · H2O (5) (H2BIPA = 5-bromoisophthalic acid, H2BDC = terephthalic acid, pdon = 1,10-phenanthroline-5,6-dione, daf = 4,5-diaza-fluoren-9-one), have been constructed from cadmium(II) salts with multi-carboxylate ligands and pdon ligands under different reaction pH. The framework structures of these polymeric complexes have been determined by the X-ray single crystal diffraction technique. The differences of the five metal-organic frameworks demonstrate that the reaction pH has an important effect on the structure of these complexes. The thermal analyses of these five complexes have been measured and discussed. Additionally, four complexes show strong fluorescence in the solid state at room temperature.  相似文献   

4.
《印度化学会志》2021,98(9):100125
A new Cu(II) coordination framework {[Cu(4-abpt)(μ3-SO42-)(H2O)]·3H2O} (1) based on the Cu–SO42- inorganic layer and the bent dipyridyl ligand was obtained under solvothermal conditions (4-abpt ​= ​4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole). The compound displays a three-dimensional (3D) “pillar-layer” framework, which can be simplified into a 3,5-connected gra topology. Furthermore, the magnetic properties of 1 have been investigated. As a result, compound 1 displays a weak antiferromagnetic interaction among the Cu(II) centers.  相似文献   

5.
A long N-heterocyclic ligand, 2,6-bis(3-(pyrid-3-yl)-1,2,4-triazolyl)pyridine (H2bptp), and Zn(II)/Pb(II) yield {[Zn(bptp)(H2O)]?·?2H2O·CH3CN} n (1) and {[Pb(bptp)]?·?H2O} n (2). Single-crystal X-ray diffraction analysis reveals that 1 and 2 possess 2-D networks containing alternating left- and right-handed helical motifs. Topologically, 1 features a (4,4) topology, while 2 exhibits a (6,3) topology. The bptp2? in 1 and 2 adopts syn-anti and syn-syn conformations, respectively. The results indicate that the long rigid N-heterocyclic ligand can adopt different conformations to coordinate with metals, beneficial to construction of helical structures with diverse topologies. The difference between the photoluminescence properties of the two complexes reveals that metal ions and coordination environment have significant influences on photoluminescence behavior.  相似文献   

6.
It is of interest that the hydrous 3D metal-organic framework (MOF) {[Pb2(fum)2(H2O)4] · 2H2O}n (1) has been synthesized by the reaction of the fum dianion with the lead(II) ion (fum = fumarate) in the presence of pyrazole, while the anhydrous 3D MOF [Pb(fum)]n (2) is obtained by the reaction of the fum dianion with the lead(II) ion in the presence of pyrazine. These complexes were further characterized by FT-IR spectroscopy, thermogravimetric analysis (TG), X-ray analysis and solid state photoluminescence spectra. The arrangement of the ligands displays a coordination gap around the Pb atom, occupied possibly by a stereoactive lone pair of electrons on lead(II), with the coordination around both the eight-coordinated lead atom in 1 and six-coordinated lead atom in 2 exhibiting a hemidirected geometry. The fum ligand shows different ligation behavior toward the lead(II) ions in these complexes. These compounds exhibit photoluminescence with the maximum emission located in the UV region.  相似文献   

7.
Two pairs of isostructural transition metal coordination polymers, {[Co(L)(H2O)]n} (1) and {[Zn(L)(H2O)]n} (3), {[Co(L)(4,4′-bipy)(H2O)]·H2O}n (2) and {[Zn(L)(4,4′-bipy)(H2O)]·H2O}n (4) (H2L = N-pyrazinesulfonyl-glycine acid and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental and thermogravimetric analyses. The structures show that 1 and 3 display 2-D polymeric grid frameworks with a 3-connected (4, 82) topology. 2 and 4 also exhibit a 2-D polymeric grid structure, but are constructed by a 4-connected (4, 4) topology. The adjacent 2-D polymeric grid frameworks for 1–4 are further linked by hydrogen bonding O–H?O interactions to form 3-D supramolecular interweaved orderly networks. The fluorescent properties of 3 and 4 were investigated in the solid state.  相似文献   

8.
Solvothermal syntheses of Cd(NO(3))(2)·4H(2)O and R-isophthalic acids (R = H, OH and t-Bu) in the presence of Ca(II) or Sr(II) lead to four new three-dimensional Cd(II)/Ca(II) or Cd(II)/Sr(II) heterometallic frameworks: [CdCa(m-BDC)(2)(DMF)(2)] (1), [CdSr(2)(m-BDC)(2)(NO(3))(2)(DMF)(4)] (2), [CdCa(OH-m-BDC)(2)(H(2)O)(2)]·2Me(2)NH (3), and (Me(2)NH(2))(2)[Cd(2)Ca(Bu(t)-m-BDC)(4)] (4) (m-H(2)BDC = isophthalate, OH-m-H(2)BDC = 5-hydroxyisophthalate and Bu(t)-m-H(2)BDC = 5-butylisophthalate). All of these compounds except for 4 crystallize in acentric (or chiral) space groups and the bulk materials for 1 and 3 display strong powder SHG efficiencies, approximately 1.54 and 2.31 times than that of a potassium dihydrogen phosphate (KDP) powder. Topological analyses show that 1 and 2 have structures with sxb and dia topologies, respectively, while both 3 and 4 exhibit pcu topological nets when the metal carboxylate clusters are viewed as nodes. The fluorescence properties and thermal stabilities for these compounds are also investigated.  相似文献   

9.
Three coordination polymers containing Cd(II) and Co(II), connected via 4-[(3-pyridyl)methylamino]benzoate (L?), have been synthesized in hydrothermal conditions. In [Cd(L)Cl] n (1), adjacent Cd(II) cations are linked by carboxylates to give a dinuclear cluster. Pairs of L? bridge the dinuclear cluster to form double helical chains, and these chains are further linked by Cl? to produce a 4-connected net with (42?·?63?·?8) topology. [CdL2] n (2) contains 1-D ladder-like chains. The packing structure displays a 3-D supramolecular structure, with π?···?π interactions stabilizing the framework. [CoL2] n (3) has a 2-D extended supramolecular structure via π?···?π interactions of 1-D coordination polymers of 3. The crystal structures of 1–3 have been determined by single-crystal X-ray diffraction. Luminescent properties for 1 and 2 are discussed.  相似文献   

10.
Two coordination polymers,{[Cu_3(tci)_2(DMAc)_3]-6DMAc 2H_2O}_n(1) and {[Cu_3(tci)_2(tpt)_2(H_2O)_2].2DMAc-2H_2O}_n(2)(H_3tci = tris(2-carboxyethyI)isocyanurate,tpt = 2,4,6-tris(4-pyridyl)-l,3,5-triazine,DMAc = N,/V-dimethylacetamide),have been constructed under solvothermal conditions.Both polymers were structurally characterized by single crystal X-ray diffraction,elemental analyses,IR spectra,thermogravimetric(TG) analyses and powder X-ray diffraction(RXPD).1 shows a(3,4)-connected 2D layer structure comprising Cu_2(CO_2)4 paddle-wheel units,which are further bridged by C-H…O interactions to give a 3D supramolecular network.The introduction of tpt produces different framework for 2 that comprises a dinuclear and a mononuclear Cu(Ⅱ) building units,which are further bridged together by tci~(3-) and tpt ligands to give a 4-connected 2D topological net.Adjacent 2D layers are packed together via C-H…O interactions and π…π stacking interactions to form a 3D supramolecular structure.In addition,the luminescent properties and the solid-state UV-vis spectra of 1 and 2 were explored.Furthermore,antiferromagnetic exchange interactions were unveiled in the Cu_2(COO)_4 units of 1.  相似文献   

11.
The new dipyridyl ligands N,N′-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide), L1, and N,N′-(methylenedi-p-phenylene)bis(pyridine-3-carboxamide), L2, incorporating amide spacers have been synthesized and reacted with metal salts to give complexes of the types [Cu(L1)2X2] (X = Cl, 1 and X = Br, 2), {[Cu(L1)2(DMF)](NO3)2}, 3, {[Ag2(L1)2](SO4)}, 4, and {[Cu(L2)(DMSO)2(NO3)](NO3)}, 5. All compounds have been characterized by spectroscopic methods and their structures determined by X-ray crystallography.Complexes 1, 2 and 3 form 1-D double-stranded polymeric chains showing rhombic molecular squares with approximate dimensions of 16.95 × 19.13 Å2 for 1, 17.03 × 19.06 Å2 for 2 and 16.66 × 19.94 Å2 for 3. Complex 4 forms infinite 1-D zigzag polymeric chains, which are interlinked through a series of Ag–O interactions to form wavy 1-D ladder like chains, and complex 5 forms 1-D sinusoidal chains. While the L1 ligands in complexes 1, 2 and 3 adopt the cis conformation and that in complex 4 adopts trans conformation, the L2 ligand in complex 5 adopts the trans-anti conformation. The ligand conformations also differ in the dihedral angles between the pyridyl and phenyl rings. All complexes exhibit emissions which may be tentatively assigned as intraligand (IL) π → π* transition.  相似文献   

12.
Several new 1D coordination polymers have been synthesised using the anionic ligand carbamoyldicyanomethanide, C(CN)2(CONH2) (cdm). The polymeric complexes [Cu(cdm)2(py)2]·2MeOH (1), [Cu(cdm)2(4-Etpy)2]·2MeOH (2), [Cu(cdm)2(3,5-Me2pzH)2]·2MeOH (3) and [Cu(cdm)2(3-HOCH2py)2]·2MeOH (4) (py = pyridine; 3,5-Me2pzH = 3,5-dimethylpyrazole) contain Cu(II) atoms bridged by μ2-(N,N′) cdm ligands between equatorial and axial coordination sites. The use of monodentate co-ligands brings about polymeric products, in contrast to the use previously of chelating co-ligands which facilitate the formation of discrete products. These 1D polymeric complexes are connected by hydrogen bonding between the amide functionalities and the lattice solvent. In the structures of 3 and 4 the neutral ligands also contain hydrogen bond donor groups that supplement the amide ring motif. Two other complexes have been obtained that are polymeric chains of alkoxide-bridged Cu(II) dimers. The complexes [Cu(cdm)(MeO)(2-amp)] (5) and [Cu(cdm)(dmap)] (6) (2-amp = 2-(aminomethyl)pyridine and dmap = dimethylaminopropoxide) are remarkably similar despite the different ligands that they contain. Bridging between dimers is via μ2-(N,O) cdm ligands, consequently altering the nature of the hydrogen bonding between adjacent chains compared to the simple polymeric species 13.  相似文献   

13.
A macrocyclic ligand L with two diethylenetriamine units linked by two rigid biphenylene spacers was used as building block for construction of metal-organic frameworks. A silver(I) complex with macrocyclic and open-chain mix-type ligands [Ag2(L)(L′)](ClO4)2 (1) [L′=1,6-bis(4-imidazol-1′-ylmethylphenyl)-2,5-diazahexane] was obtained by reaction of L and L′ together with AgClO4·H2O. It is interesting that the open-chain tetradentate ligand L′ only served as a bidentate ligand to bridge the Ag2L units into an infinite one-dimensional (1D) cationic chain. Neutral 1D chain coordination polymer [Cu2(L)(μ-SO4)2]·3H2O·3MeOH (2) is formed by sulfate bridges between the neighboring Cu2L units. When L reacted with nickel(II) sulfate instead of copper(II) sulfate, a monomacrocycle molecular complex [Ni2(L)(H2O)4(SO4)2] (3) was obtained in which the sulfate anion acts as monodentate ligands rather than as bridges. When Cd(II) salts were used for the reactions with L, another two neutral 1D coordination polymers, [Cd2(L)(μ-Cl)2Cl2]·2H2O (4) and [Cd2(L)(μ-Br)2Br2] (5), with the same structure were isolated. All the synthesized complexes exhibit three-dimensional framework structures linked by various hydrogen bonds. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature, and the Ag(I) and Cd(II) complexes were found to show strong blue luminescence.  相似文献   

14.
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   

15.
The coordination polymers, [Ni(L)2]n ( 1 ) and [Mn2(L)2(DMF)2(H2O)]n ( 2 ) were synthesized by using a tritopic ligand 5‐(4′‐carboxylphenoxy)nicotinic acid (H2L). The structural analysis shows that compound 1 exhibits a ten‐connected three‐dimensional (3D) architecture with the point symbol 312.426.57, 2 displays an eight‐connected topology network with a point symbol of 424.64. The structures and formulas of 1 and 2 were determined by X‐ray diffraction, elemental analysis, and thermogravimetric analysis (TGA). In addition, the magnetic behaviors for 1 and 2 were investigated.  相似文献   

16.
In this article, ten new coordination frameworks, namely, [Ni(H2O)6]·(L3) (1), [Zn(L3)(H2O)3] (2), [Cd(L3)(H2O)3]·5.25H2O (3), [Ag(L1)(H2O)]·0.5(L3) (4), [Ni(L3)(L1)] (5), [Zn(L3)(L1)0.5]·H2O (6), [Cd(L3)(L1)0.5(H2O)] (7), [CoCl(L3)0.5(L1)0.5] (8), [ZnCl(L3)0.5(L2)0.5] (9), and [CoCl(L3)0.5(L2)0.5] (10), where L1 = 1,1′-(1,4)-butanediyl)bis(imidazole), L2 = 1,1′-(1,4-butanediyl)bis(2-ethylbenzimidazole) and H2L3 = 3,3′-(p-xylylenediamino)bis(benzoic acid), have been synthesized by varying the metal centers and nitrogen-containing secondary ligands. These structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses and IR spectra. In 1, the L3 anion is not coordinated to the Ni(II) center as a free ligand. The Ni(II) ion is coordinated by water molecules to form the cationic [Ni(H2O)6]2+ complex. The hydrogen bonds between L3 anions and [Ni(H2O)6]2+ cations result in a three-dimensional (3D) supramolecular structure of 1. In compounds 2 and 3, the metal centers are linked by the organic L3 anions to generate 1D infinite chain structures, respectively. The hydrogen bonds between carboxylate oxygen atoms and water molecules lead the structures of 2 and 3 to form 3D supramolecular structures. In 4, the L3 anion is not coordinated to the Ag(I) center, while the L1 ligands bridge adjacent Ag(I) centers to give 1D Ag-L1 chains. The hydrogen bonds among neighboring L3 anions form infinite 2D honeycomb-like layers, in the middle of which there exist large windows. Then, 1D Ag-L1 chains thread in the large windows of the 2D layer network, giving a 3D polythreaded structure. Considering the hydrogen bonds between the water molecules and L3 anions, the structure is further linked into a 3D supramolecular structure. Compounds 5 and 7 were synthesized through their parent compounds 1 and 3, respectively, while 6 and 9 were obtained by their parent compound 2. In 5, the L3 anions and L1 ligands connect the Ni(II) atoms to give a 3D 3-fold interpenetrating dimondoid topology. Compound 6 exhibits a 3D three-fold interpenetrating α-Po network structure formed by L1 ligands connecting Zn-L3 sheets, while compound 7 shows a 2D (4,4) network topology with the L1 ligands connecting the Cd-L3 double chains. In compound 8, the L1 ligands linked Co-L3 chains into a 2D layer structure. Two mutual 2D layers interpenetrated in an inclined mode to generate a unique 3D architecture of 8. Compounds 9 and 10 display the same 2D layer structures with (4,4) network topologies. The effects of the N-containing ligands and the metal ions on the structures of the complexes 1-10 were discussed. In addition, the luminescent properties of compounds 2-4, 6, 7 and 9 were also investigated.  相似文献   

17.
Four Cd(II)- and Cu(II)-containing coordination polymers (CPs) based on a multidentate N-donor ligand and varied dicarboxylate anions, [Cd(3,3′-tmbpt)(p-bdc)]·2.5H2O (1), [Cd(3,3′-tmbpt)(m-bdc)]·2H2O (2), [Cu(3,3′-tmbpt)(m-bdc)]·H2O (3), and [Cu(3,3′-tmbpt)(p-bdc)]·2H2O (4), where 3,3′-tmbpt = 1 ? ((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, p-H2bdc = 1,4-benzenedicarboxylic acid, and m-H2bdc = 1,3-benzenedicarboxylic acid, have been prepared hydrothermally. The structures of the compounds were determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra and elemental analyses. Compound 1 exhibits a 3-D twofold interpenetrating framework with a 65·8 CdSO4 topology. Compound 2 is a 2-D layer containing meso-helical chains with a 44·62 sql topology. Compound 3 shows a 1-D → 3-D interdigitated architecture while 4 displays a 2-D → 3-D interdigitated architecture. The structural differences of the compounds indicate that the dicarboxylate anions and the central metal ions play important roles in the resulting structures of CPs. Optical band gaps and solid-state photoluminescent properties have also been studied.  相似文献   

18.
《中国化学快报》2019,30(11):1931-1934
By applying two donor-acceptor motif molecules, 5,10-di(pyridin-4-yl)-5,10-dihydrophenazine (L1) and 10,10'-di(pyridin-3-yl)-10H,10'H-9,9'-spiroacridine (L2), as ligands and CuI/AgCF3CO2 as metal salt, we synthesized three coordination polymers, namely, {Cu4(L1)2I4} (CP1), {Cu(L2)I·CHCl3} (CP2) and {Ag(L2)CO2CF3·CHCl3} (CP3). X-ray crystallographic analysis revealed that three coordination polymers all feature one-dimensional (1D) linear chains which are consisting of molecular boxlike units. In comparison with low photoluminescence quantum yield (PLQY) of two ligands, three coordination polymers, CP1, CP2 and CP3, present more intense photoluminescence with PLQY of 15%, 46% and 34% at room temperature respectively. The PL emission of CP1 and CP2 at room temperature could be attributed to the fast phosphorescence with lifetime both around 5 μs due to effective intersystem crossing (ISC). Whilst, it is worth noting that CP3 exhibit thermally activated delayed fluorescence (TADF) emission at room temperature.  相似文献   

19.
Three luminescent Cu (I) and Ag (I) coordination polymers based on donor-acceptor motif ligands are reported.Two Cu (I) coordination polymers both exhibit fast phosphorescence,which another Ag (I) coordination polymer present TADF photoluminescence emission at room temperature.  相似文献   

20.
Three novel polymers, {[Cd(m-bdc)(L)]·H2O}n (1), [Co(m-bdc)(L)0.5(H2O)]n (2) and [Zn5(L)2(p-bdc)5(H2O)]n (3) based on 1,1′-bis(pyridin-3-ylmethyl)-2,2′-biimidazole (L) ligand and benzenedicarboxylate isomers, have been prepared and structurally characterized. Compound 1 exhibits a 2D architecture with (42·6)(42·67·8) topology, which is synthesized by L and 1,3-benzenedicarboxylate (m-bdc) ligands. Compound 2 is constructed from 1D chains that are linked by L ligands extending a 2D (4,4) grid. Compound 3 is a 3D framework with (43)(46·618·84) topology, which is composed of trinuclear clusters and five-coordinated metal centers joined through 1,4-benzenedicarboxylate (p-bdc) and L ligands. Moreover, the fluorescent properties of L ligand, compounds 1 and 3 are also determined.  相似文献   

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