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1.
First examples of transition metal complexes with HpicOH [Cu(picOH)2(H2O)2] ( 1 ), [Cu(picO)(2,2′‐bpy)]·2H2O ( 2 ), [Cu(picO)(4,4′‐bpy)0.5(H2O)]n ( 3 ), and [Cu(picO)(bpe)0.5(H2O)]n ( 4 ) (HpicOH = 6‐hydroxy‐picolinic acid; 2,2′‐bpy = 2,2′‐bipyridine; 4,4′‐bpy = 4,4′‐bipyridine; bpe = 1,2‐bis(4‐pyridyl)ethane) have been synthesized and characterized by single‐crystal X‐ray diffraction. The results show that HpicOH ligand can be in the enol or ketonic form, and adopts different coordination modes under different pH value of the reaction mixture. In complex 1 , HpicOH ligand is in the enol form and adopts a bidentate mode. While in complexes 2 – 4 , as the pH rises, HpicOH ligand becomes in the ketonic form and adopts a tridentate mode. The coordination modes in complexes 1 – 4 have not been reported before. Because of the introduction of the terminal ligands 2,2′‐bpy, complex 2 is of binuclear species; whereas in complexes 3 and 4 , picO ligands together with bridging ligands 4,4′‐bpy and bpe connect CuII ions to form 2D nets with (123)2(12)3 topology.  相似文献   

2.
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   

3.
Two coordination polymers, {[Zn2(L)(bpy)] · 2H2O}n ( 1 ) and [Zn2(L)(bpe)]n ( 2 ) [H4L = terphenyl‐2,2′,4,4′‐tetracarboxylic acid, bpy = 4,4′‐bipyridine, and bpe = 1,2‐bis(4‐pyridyl)ethane], were hydrothermally synthesized under similar conditions and characterized by elemental analysis, IR spectroscopy, TGA, and single‐crystal X‐ray diffraction analysis. Compound 1 has a 3D framework containing Zn–O–C–O–Zn 1D chains. Compound 2 exhibits a 3D framework, which features tubular channels. The channels are occupied by bpe molecules. The differences in the structures demonstrate that the auxiliary dipyridyl‐containing ligand has a significant effect on the construction of the final framework. Additionally, the fluorescent properties of the two compounds were also studied in the solid state at room temperature.  相似文献   

4.
在水热条件下, 以6-羟基-2-吡啶基膦酸为主配体, 4, 4'-联吡啶(bpy)及1, 2-二(4-吡啶基)乙烯(bpe)为桥联配体, 合成了2个铜膦酸配位聚合物[Cu3(L)2(bpy)2(H2O)2]·2H2O (1), [Cu3(L)2(bpy)2(H2O)3]·2H2O (2)。配合物1中, Cu2+离子由膦酸配体连接成一条链, 该链由bpy桥联成二维层, 层与层之间通过氢键作用构成三维结构。配合物2与配合物1是同构的, 桥联配体是bpe。磁性研究表明, 配合物12中铜离子之间存在反铁磁性耦合。  相似文献   

5.
在水热条件下, 以6-羟基-2-吡啶基膦酸为主配体, 4, 4′-联吡啶(bpy)及1, 2-二(4-吡啶基)乙烯(bpe)为桥联配体, 合成了2个铜膦酸配位聚合物[Cu3(L)2(bpy)2(H2O)2]· 2H2O (1), [Cu3(L)2(bpy)2(H2O)3]· 2H2O (2)。配合物1中, Cu2+离子由膦酸配体连接成一条链, 该链由bpy桥联成二维层, 层与层之间通过氢键作用构成三维结构。配合物2与配合物1是同构的, 桥联配体是bpe。磁性研究表明, 配合物12中铜离子之间存在反铁磁性耦合。  相似文献   

6.
Three new ZnII coordination polymers, [Zn(bpe)(HL)2(H2O)]n ( 1 ), {[Zn(bpe)(L)] · H2O}n ( 2 ), and [Zn2Ca(bpe)(HL)2(L)2]n ( 3 ) [H2L = 5‐methoxyisophthalic acid and bpe = 1,2‐dis(4‐pyridyl) ethylene], were hydrothermally synthesized under different pH values and bases. Their structures were determined by single‐crystal X‐ray diffraction and further characterized by elemental analyses and IR spectroscopy. Polymer 1 is formed at pH = 4 and has a 1D chain structure. These 1D chains are linked by hydrogen bonds to afford a 1D double chain and further to form a threefold interpenetrating network. At pH = 7, a 2D layer structure of 2 with sql topology is formed. By using calcium hydroxide as base for the synthesis of 3 , a 3D network with pcu topology is obtained. These structural differences among 1 – 3 indicate that pH value and the identity of the base play important role in defining the overall structures of metal‐organic frameworks. In addition, the fluorescent properties of 1 – 3 are discussed.  相似文献   

7.
Two new tetranuclear cluster-based compounds, namely [Cd2(L1)(H2O)(DMA)]n ( 1 ) and [Cd2Ba2(L2)(H2O)6(DMA)]n ( 2 ) [H4L1 = 3-(3',5'-dicarboxylphenoxy) phthalic acid, H4L2 = 6-(3',4'-dicarboxyl-phenoxy) isophthalic acid, DMA = N,N'-dimethylacetamide], were successfully synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analyses. Compound 1 features a two-dimensional (2D) layered framework with tetranuclear [Cd4(COO)6] clusters as building subunits, and can be simplified into a binodal (3, 6)-connected kgd topological network with the schläfli symbol of {43}2{46;66;83}, and compound 2 features a three-dimensional (3D) complicated framework based on heterometallic tetranulear [Cd2Ba2(COO)8] cluster subunits, and can be simplified into a binodal (3, 6)-connected topological network. In addition, compounds 1 and 2 not only have high thermal stabilities but also show strong luminescent emissions at room temperature.  相似文献   

8.
Four novel mixed‐ligand complexes were obtained from the reaction of maleic acid, diimine chelating ligands and Cd(OH)2 or CdO in a mixed solvent of water and methanol. The complexes were characterized by IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. The results show that all the four complexes are coordination polymers. [Cd(phen)(H2O)(male)]n · 2nH2O ( 1 ) and [Cd(bipy)(H2O)(male)]n · 2nH2O ( 2 ) (male = maleate; phen = 1, 10‐phenanthroline, bipy = 2, 2′‐bipyridine) are isomorphic, and the asymmetric unit is constructed by one CdII atom, a maleate group, a diimine ligand and two crystal water molecules. Each maleate group links two CdII atoms in a bis(bidentate) chelating mode, resulting in a 1D helical chain. Within [Cd(phen)(H2O)2(male)]n · 2nH2O ( 3 ), the maleate group bridges two CdII atoms in a bis(monodentate) chelating mode into a 1D helical chain along the [100] direction. The helical chain is decorated by phen groups alternatively at the two sides, and each phen plane of one chain is inserted in the void space between two adjacent phen ligands from an adjacent chain, resulting in a double zipper‐like chain. The asymmetric unit of [Cd2(phen)2(male)2]n ( 4 ) contains a CdII cation, one phen molecule, and a maleate group, and one bridging maleate group links three CdII atoms resulting in a 2D layer extending in [011] plane. The 2D networks are constructed by four kinds of rings formed by the central metal atom and maleate dianion. The thermostabilities of the four complexes were investigated.  相似文献   

9.
A Ligand-Directed strategy has been adopted to synthesize three novel Copper(І) coordination polymers, [Cu2(bpe)(N3)2] n (1), [Cu2(bpy)(N3)2] n (2), and [Cu4(py)(N3)4] n (3), by the reactions of NaN3 with bpe, bpy and py (bpe = 1,2-trans-(4-pyridyl)ethene, bpy = 4,4′-bipyridine, py = pyrazine) in the presence of H3PO3 under hydrothermal conditions, which proved that the length of ligands had subtle effects on overall network and the coordination mode of azide.  相似文献   

10.
Two new nickel(II) complexes, [Ni(4, 4′‐bpy)(H2O)4]n · n(cpp) · 0.5nH2O ( 1 ) and [Ni(cpp)(4, 4′‐bpy)(H2O)2]n ( 2 ) [4, 4′‐bpy = 4, 4′‐bipyridine, H2cpp = 3‐(4‐carboxyphenyl)propionic acid] were synthesized and characterized by single‐crystal X‐ray diffraction, elemental analysis, IR spectroscopy, and thermal analysis. In complex 1 , NiII ions are bridged by 4, 4′‐bpy into 1D chains, and cpp ligands are not involved in the coordination, whereas in complex 2 , cpp ligands adopt a bis(monodentate) mode and link NiII ions into 2D (4, 4) grids with the help of 4, 4′‐bpy ligands. Triple interpenetration occurs, which results in the formation of a complicated 3D network. The difference in the structures of the two complexes can be attributed to the different reaction temperatures and bases.  相似文献   

11.
Two new coordination polymers, {[Cd2(btc)(2,2′‐bpy)2] · H2O}n ( 1 ) and [Zn2(btc)(2,2′‐bpy)(H2O)]n ( 2 ) (H4btc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine), were synthesized hydrothermally under similar conditions and characterized by elemental analysis, IR spectra, TGA, and single‐crystal X‐ray diffraction analysis. In complexes 1 and 2 , the (btc)4– ligand acts as connectors to link metal ions to give a 2D bilayer network of 1 and a 3D metal‐organic framework of 2 , respectively. The differences in the structures are induced by diverging coordination modes of the (btc)4– ligand, which can be attributed to the difference metal ions in sizes. The results indicate that metal ions have significant effects on the formation and structures of the final complexes. Additionally, the fluorescent properties of the two complexes were also studied in the solid state at room temperature.  相似文献   

12.
Based on 5-mercapto-1H-tetrazole-1-methanesulfonic acid disodium salt (Na2mtms) and 4,4′-bipyridine (bpy) as ligands, four new transition metal complexes, namely {[Cd2(mtms)(bpy)2(OAc)2]·H2O} n (1), {[Cd(mtms)(bpy)2(H2O)2]2·bpy·4H2O} n (2), {[Zn2(μ 2-OH)(mtms)(bpy)3(H2O)]·ClO4·H2O} n (3), and {[Co(mtms)2(bpy)(H2O)2]·[Co(bpy)2(H2O)4]·H2O} n (4), have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1 features a pillared-layer coordination architecture linked by acetate, mtms, and bridging bpy ligands. Complex 2 has a 1D polymeric structure with [Cd(mtms)(bpy)2(H2O)2] as the repeating unit; these infinite chains are further connected into a 3D supramolecular framework through π–π stacking of bpy ligands. In complex 3, the mtms ligand combined with μ 2-OH bridges two Zn atoms to form a dimer structure, which is different from that of complex 2. Complex 4 shows a 3D supramolecular network containing infinite [Co(mtms)2(bpy)(H2O)2]2? anionic chains and free [Co(bpy)2(H2O)4]2+ cationic components. The luminescence properties of 1 and 2 and the electrochemical properties of 3 are reported.  相似文献   

13.
Colourless crystals of the title compound, [Cd2(C7H4IO2)4(C12H10N2)(H2O)2]n, were obtained by the self‐assembly of Cd(NO3)2·4H2O, 1,2‐bis(pyridin‐4‐yl)ethene (bpe) and 4‐iodobenzoic acid (4‐IBA). Each CdII atom is seven‐coordinated in a pentagonal–bipyramidal coordination environment by four carboxylate O atoms from two different 4‐IBA ligands, two O atoms from two water molecules and one N atom from a bpe ligand. The CdII centres are bridged by the aqua molecules and bpe ligands, which lie across centres of inversion, to give a two‐dimensional net. Topologically, taking the CdII atoms as nodes and the μ‐aqua and μ‐bpe ligands as linkers, the two‐dimensional structure can be simplified as a (6,3) network.  相似文献   

14.
Four CdII metal coordination polymers, namely, [Cd(HL)(H2O)3]n ( 1 ), [Cd(HL)(4,4′‐bpy)]n · nH2O ( 2 ), [Cd3(L)2(2,2′‐bpy)3(H2O)3]n · 2nH2O ( 3 ), and [Cd3(L)2(phen)2(H2O)]n · 2.5nH2O ( 4 ) [H3L = 3‐(3‐carboxyphenoxy) phthalic acid, 4,4′‐bpy = 4,4′‐bipyridine, 2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline], were synthesized and structurally characterized by X‐ray diffraction, elemental analysis, and IR spectroscopy. Single‐crystal X‐ray analyses reveal that complexes 1 – 3 have different one‐dimensional (1D) chain structures including zigzag chain, ladder chain, and helical chain, whereas complex 4 shows a 0D trinuclear motif. These low‐dimensional complexes are further extended to 3D supramolecular networks by intermolecular π–π interactions and hydrogen bonds. The ligand H3L exhibits five coordination modes: μ1‐η2‐chelating/μ1‐η2‐chelating, μ1‐η2‐chelating/μ1‐η2‐chelating/μ1‐η2‐chelating, μ1‐η2‐chelating/μ1‐η2‐chelating/μ1‐η1‐bridging, μ1‐η2‐chelating/μ2‐η2‐bridging/μ2‐η11‐bridging, and μ2‐η2‐chelating:η1‐bridging/μ2‐η2‐chelating:η1‐bridging/μ1‐η1‐bridging. Moreover, the photoluminescent properties of complexes 1 – 4 were studied in the solid‐state at room temperature.  相似文献   

15.
Three new supramolecular compounds were synthesized and characterized with the formula of [Zn4(picO)4(phen)4]·11.25H2O ( 1 ), [Zn4(picO)4(2,2′‐bpy)4(H2O)4]·12H2O ( 2 ), and [Zn3(picO)3(bpe)5(H2O)3]n·8.5nH2O ( 3 ) (H2picO = 6‐hydroxypicolinic acid; phen = 1,10‐phenanthroline; 2,2′‐bpy = 2,2′‐bipyridine; bpe = 1,2‐bis(4‐pyridyl)ethane). For complexes 1 and 2 , picO ligands adopt tridentate, tetradentate and bidentate coordination modes to link zinc(II) ions into dimers, which are extended into 3D supramolecular structures through hydrogen bonds. Water chains with cyclic page‐like octamer and boat‐like heptamer water clusters are included, respectively. Complex 3 is of a 2D brick‐wall structure. Triple interpenetration occurs, and there are still cyclic chair‐like octamer water clusters in the channels. The fluorescent properties of complexes 1‐3 have also been investigated.  相似文献   

16.
The reactions of transition metal salts or hydroxide with 1,4‐phenylenediacetic acid (H2PDA) in the presence of ancillary ligands 4,4′‐bipyridine (4,4′‐bpy) or imidazole (Im) produced five coordination polymers with the empirical formula [M(PDA)(4,4′‐bpy)(H2O)2]n [M = Mn ( 1 ), Ni ( 2 )], [Cu(PDA)(4,4′‐bpy)]n · 2nH2O ( 3 ), [Ni(PDA)(Im)2(H2O)2]n · nH2O ( 4 ), and [Cu(PDA)(Im)2]n · 2nH2O ( 5 ). Their structures were determined by single‐crystal X‐ray diffraction analyses. The isomorphous 1 and 2 present a two‐dimensional sheet constructed by two kinds of one‐dimensional chains of –NiII–PDA2––NiII– and –NiII–4,4′‐bpy–NiII–. Compound 3 features dinuclear subunits, which are further connected by two PDA2– ligands and two 4,4′‐bpy ligands along (001) and (011) directions, respectively, to build a two‐dimensional sheet with the topology (42.67.8)(42.6) different from those of 1 and 2 . Both 4 and 5 show one‐dimensional chain structure. The difference of compound 4 and 5 is that the two carboxylato groups of PDA2– in 4 adopt monodentate coordination modes, whereas the two carboxylato groups of PDA2– in 5 chelate to the metal ions. Magnetic susceptibility data of 1 were measured. Magnetically, 1 presents a one‐dimensional chain with a weak antiferromagnetic interaction (J =–0.064 cm–1) between the intrachain MnII atoms mediated by 4,4′‐bpy.  相似文献   

17.
Two new compounds, [Ag(Hppdb)]n ( 1 ) and {[Ag2(Hppdb)2(bpe)] · 5.5H2O}n( 2 ) [H2ppdb = [2,3‐f]pyrazino[1,10]phenanthroline‐2,3‐dicarboxylic acid, bpe = trans‐1,2‐bis(4‐pyridyl)ethylene], were synthesized and characterized. In 1 , Hppdb ions link AgI cations to form an infinite 1D [–Ag–(Hppdb)–Ag–]n chain, furthermore, the dimensionality is extended to 2D layers through synergistic π–π stacking, hydrogen‐bonding and weak Ag ··· O interactions. Correspondingly, the dimeric [(Ag)(Hppdb)]2 subunits in 2 are connected by bpe ligands to generate a loop‐link‐shaped 1D chain motif, which is further joined through a R22(18)C–H ··· O hydrogen‐bonding ring to afford interesting diagonal/diagonal inclined catenation 2D + 2D → 3D supramolecular architectures. In addition, solid‐state properties such as photoluminescence and thermal stability of the two compounds were studied.  相似文献   

18.
Hydrothermal reactions of cadmium nitrate and 4‐pyridylnicotinamide (4‐pna) with a 5‐substituted isophthalic acid derivative afforded four coordination polymers, whose structural chemistry depends on the nature of the substituent. The crystalline phases produced using bromo and carboxylic acid substituents, [Cd(Brip)(4‐pna)]n ( 1 ) (Brip = 5‐bromoisophthalate) and [Cd(Hbtc)(4‐pna)]n ( 2 ) (btc = 1,3,5‐benzenetricarboxylate), have similar structural chemistry. They both exhibit anti‐syn {Cd2(OCO)2} dimeric units that serve as 6‐connected nodes for 3D twofold interpenetrated 41263 pcu networks, which are constructed by the linkage of [Cd2(carboxylate)2]n ribbons by tethering 4‐pna ligands. An in situ amide hydrolysis of the 4‐pna precursor was observed when a bulkier substituent (tert‐butyl or methoxy) was utilized. The resulting nicotinate (nic) anions were incorporated into {[Cd2(tbip)(nic)2(H2O)4] · H2O}n ( 3 ) (tbip = 5‐tert‐butylisophthalate) and [Cd2(meoip)(nic)2(H2O)2]n ( 4 ) (meoip = 5‐methoxyisophthalate) which both display an overall (6,3) hexagonal grid layered topology. However, 3 shows isolated cadmium atoms while 4 manifests {Cd2(OCO)2} anti‐syn bridged dimeric clusters. Luminescent and thermal properties of these materials are also reported.  相似文献   

19.
A series of binuclear complexes [{Cp*Ir(OOCCH2COO)}2(pyrazine)] ( 1 b ), [{Cp*Ir(OOCCH2COO)}2(bpy)] ( 2 b ; bpy=4,4′‐bipyridine), [{Cp*Ir(OOCCH2COO)}2(bpe)] ( 3 b ; bpe=trans‐1,2‐bis(4‐pyridyl)ethylene) and tetranuclear metallamacrocycles [{(Cp*Ir)2(OOC‐C?C‐COO)(pyrazine)}2] ( 1 c ), [{(Cp*Ir)2(OOC‐C?C‐COO)(bpy)}2] ( 2 c ), [{(Cp*Ir)2(OOC‐C?C‐COO)(bpe)}2] ( 3 c ), and [{(Cp*Ir)2[OOC(H3C6)‐N?N‐(C6H3)COO](pyrazine)}2] ( 1 d ), [{(Cp*Ir)2[OOC(H3C6)‐N?N‐(C6H3)COO](bpy)}2] ( 2 d ), [{(Cp*Ir)2[OOC(H3C6)‐N?N‐(C6H3)COO](bpe)}2] ( 3 d ) were formed by reactions of 1 a – 3 a {[(Cp*Ir)2(pyrazine)Cl2] ( 1 a ), [(Cp*Ir)2(bpy)Cl2] ( 2 a ), and [(Cp*Ir)2(bpe)Cl2] ( 3 a )} with malonic acid, fumaric acid, or H2ADB (azobenzene‐4,4′‐chcarboxylic acid), respectively, under mild conditions. The metallamacrocycles were directly self‐assembled by activation of C? H bonds from dicarboxylic acids. Interestingly, after exposure to UV/Vis light, 3 c was converted to [2+2] cycloaddition complex 4 . The molecular structures of 2 b , 1 c , 1 d , and 4 were characterized by single‐crystal x‐ray crystallography. Nanosized tubular channels, which may play important roles for their stability, were also observed in 1 c , 1 d , and 4 . All complexes were well characterized by 1H NMR and IR spectroscopy, as well as elemental analysis.  相似文献   

20.
The coordination polymers (CPs), [Ni(L)(H2O)4]n ( 1 ), [Co(HL)2(H2O)2]n ( 2 ), {[Cu(L)(H2O)3] · H2O}n ( 3 ), [Mn(L)(H2O)2]n ( 4 ), [Cd(L)(H2O)2]n ( 5 ), and {[Zn2(L)2] · H2O}n ( 6 ), were solvothermally synthesized by employing the imidazol‐carboxyl bifunctional ligand 4‐(1H‐imidazol‐1‐yl) phthalic acid (H2L). Single‐crystal X‐ray diffraction indicated that the L2–/HL ligands display various coordination modes with different metal ions in 1 – 6 . Complexes 1 and 2 show one‐dimensional (1D) chain structures, whereas complexes 3 – 6 show 2D layered structures. The magnetic properties of these complexes were investigated. Complexes 1 and 3 indicate weak ferromagnetic interactions, whereas complexes 2 and 4 demonstrate antiferromagnetic interactions. In addition, luminescence properties of 5 and 6 were measured and studied in detail.  相似文献   

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