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1.
Three coordination polymers (CPs) based on the 5‐[4‐(1H‐imidazol‐1‐yl)phenyl]‐1H‐tetrazole ( HL ) ligand, namely, [Cu(μ2‐ L )(μ4‐pbda)(H2O)] ( 1 ), [Cu2(μ‐Hbtc)(H2btc)(μ3‐OH)(μ4‐ HL )] ( 2 ) and [Cu53‐ L )(μ4‐ L )(μ3‐ip)(μ3‐OH)(H2O)2] · 2H2O ( 3 ) (H2pbda = 1,4‐benzenedicarboxylic acid, H3btc = 1,3,5‐benzenetricarboxylic acid, H2ip = isophthalic acid) were hydrothermally synthesized and structurally characterized. Complex 1 represents “weave”‐type 2D layers consisting of wave‐like 1D chains and 1D straight chains, which are further connected by hydrogen bonds to form a 3D supramolecular structure. Complex 2 exhibits a uninodal (4)‐connected 2D layer with a point symbol of {44 · 62}, in which the L ligand can be described as μ5‐bridging and the H2btc ions display multiple kinds of coordination modes to connect CuII ions into 1D “H”‐type Cu‐H2btc chains. In complex 3 , 2D Cu‐ L layers with two kinds of grids and 1D “stair”‐type Cu‐ip chains link each other to construct a 3D {412 · 63} framework, which contains the pentanuclear subunits. Deprotonated degree and coordination modes of carboxylate ligands may consequentially influence the coordination patterns of main ligands and the final structures of complexes 1 – 3 . Furthermore, electrochemical behaviors and electrocatalytic activities of the title complexes were analyzed at room temperature, suggesting practical applications in areas of electrocatalytic reduction toward nitrite and hydrogen dioxide in aqueous solutions, respectively.  相似文献   

2.
The imidazole‐based dicarboxylate ligand 2‐(4‐(pyridin‐4‐yl)phenyl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H3PyPhIDC), was synthesized and its coordination chemistry was studied. Solvothermal reactions of CaII, MnII, CoII, and NiII ions with H3PyPhIDC produced four coordination polymers, [Ca(μ3‐HPyPhIDC)(H2O)2]n ( 1 ), {[M32‐H2PyPhIDC)23‐HPyPhIDC)26(H2O)2] · 6H2O}n [M = Mn ( 2 ), Co ( 3 )], and {[Ni(μ3‐HPyPhIDC)(H2O)] · H2O}n ( 4 ). Compounds 1 – 4 were analyzed by IR spectroscopy, elemental analyses, and single‐crystal and powder X‐ray diffraction. Compound 1 displays a one‐dimensional (1D) infinite chain. Compounds 2 and 3 are of similar structure, showing 2D network structures with a (4,4) topology based on trinuclear clusters. Compound 4 has another type of 2D network structure with a 3‐connected (4.82) topology. The results revealed that the structural diversity is attributed to the coordination numbers and geometries of metal ions as well as the coordination modes and conformations of H3PyPhIDC. Moreover, the thermogravimetric analyses of all the compounds as well as luminescence properties of the H3PyPhIDC ligand and compound 1 were also studied.  相似文献   

3.
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   

4.
Hydrothermal reactions of tridentate rigid 2,4,6‐tris‐(benzimidazolyl‐2‐yl)pyridine (pytbzim) ligand and Zn(II)/Cd(II) salts generate binuclear complexes {[Cd2Cl2(pytbzim)2(H2O)2]·2NO3}n ( 1 ) and two isomorphs {[M2Cl2(pytbzim)2(H2O)2]Cl2·2H2O}n [M=Cd ( 2 ), Zn ( 3 )]. All complexes include [M2Cl2(pytbzim)2(H2O)2] dimers, which are further connected into a three‐dimensional supramolecular networks through ?‐? stacking interaction and hydrogen bonds. The solid state photoluminescent studies reveal good fluorescent properties of the pytbzim ligand and complexes 1 – 2 at room temperature.  相似文献   

5.
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   

6.
Four complexes with supramolecular architectures, namely, MZCA · 3H2O ( 1 ), [Zn(H2O)6]2+ · [MZCA]2 · [H2O]6 ( 2 ), [Mn(MZCA)2(H2O)4] · 2H2O ( 3 ), and [Ni(MZCA)2(H2O)4] · 2H2O ( 4 ) [MZCA = 3‐(carboxymethyl)‐2, 7‐dimethyl‐3H‐benzo[d]imidazole‐5‐carboxylic acid], were synthesized and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. Complexes 1 and 2 display a remarkable 3D network with 1D hydrophilic channels. Complexes 3 and 4 are isostructural and exhibit a 3D structure encapsulating 1D 24‐membered ring microporous channels. The UV/Vis and fluorescent spectra were measured to characterize complexes 1 – 4 . The thermal stability of complexes 2 – 4 were also examined.  相似文献   

7.
The design and synthesis of new organic lgands is important to the rapid development of coordination polymers (CPs). However, CPs based on asymmetric ligands are still rare, mainly because such ligands are usually expensive and more difficult to synthesize. The new asymmetric ligand 4‐[4‐(1H‐imidazol‐1‐yl)phenyl]pyridine (IPP) has been used to construct the title one‐dimensional coordination polymer, catena‐poly[[[aqua{4‐[4‐(1H‐imidazol‐1‐yl‐κN3)phenyl]pyridine}cadmium(II)]‐μ‐5‐hydroxybenzene‐1,3‐dicarboxylato‐κ3O1,O1′:O3] monohydrate], {[Cd(C8H4O5)(C14H11N3)2(H2O)]·H2O}n, under hydrothermal reaction of IPP with CdII in the presence of 5‐hydroxyisophthalic acid (5‐OH‐H2bdc). The CdII cation is coordinated by two N atoms from two distinct IPP ligands, three carboxylate O atoms from two different 5‐OH‐bdc2− dianionic ligands and one water O atom in a distorted octahedral geometry. The cationic [Cd(IPP)2]2+ nodes are linked by 5‐OH‐bdc2− ligands to generate a one‐dimensional chain. These chains are extended into a two‐dimensional layer structure via O—H…O and O—H…N hydrogen bonds and π–π interactions.  相似文献   

8.
张曙光  冯云龙 《中国化学》2009,27(5):877-881
四唑酸(–CN4H)与羧酸(–COOH)具有相似的酸性。对苯酚四唑硫酮(H2L)可以作为单齿(–S或–N)或双齿(–N, N或–N, S)配体与金属离子配位形成配位化合物。合成了4个以H2L为配体的金属(II)配合物:Co(HL)2(Py)2(H2O)2 (1), [Mn(HL)2(H2O)4]·2H2O (2), Mn(HL)2(Phen)2 (3), and [Zn(HL)2(Phen)2]·0.5H2O·1.5CH3OH (4),并用X−射线单晶衍射法测定了晶体结构。晶体结构分析表明,在这些配合物中所有的中心金属原子均呈现六配位的八面体构型。在配合物1和2中,HL–配体以氧原子与中心金属原子配位,而在配合物3和4中HL–配体则以硫原子与中心金属原子配位。  相似文献   

9.
A series of homo‐ and hetero‐trinuclear cobalt(II) complexes [Co3(L)(OAc)2(CH3CH2OH)(H2O)] ( 1 ), [Co2Ba(L)(OAc)2] ( 2 ) and [Co2Ca(L)(OAc)2]·CHCl3 ( 3 ), containing an acyclic naphthalenediol‐based ligand H4L were synthesized. All the three complexes were characterized by elemental analyses, IR, UV – vis spectra and single crystal X‐ray diffraction analyses. Comparative studies of the structures and spectroscopic properties are carried out on these complexes. All of the complexes show catechol oxidase activities in MeCN. Using UV – vis spectroscopy, we monitored the aerial oxidation of 3,5‐di‐tert ‐butylcatechol (3,5‐DTBCH2) to 3,5‐di‐tert ‐butylquinone (3,5‐DTBQ), which confirms the essential role of these complexes in enhancing the catalytic reaction.  相似文献   

10.
Crystal structures are reported for four related diethyl [(arylamino)(4‐ethynylphenyl)lmethyl]phosphonate derivatives, namely diethyl [(4‐bromoanilino)(4‐ethynylphenyl)methyl]phosphonate, C19H21BrNO3P, (I), diethyl ((4‐chloro‐2‐methylanilino){4‐[2‐(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate, C23H31ClNO3PSi, (II), diethyl ((4‐fluoroanilino){4‐[2‐(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate, C22H29FNO3PSi, (III), and diethyl [(4‐ethynylphenyl)(naphthalen‐2‐ylamino)methyl]phosphonate, C23H24NO3P, (IV). The conformation of the anilinobenzyl group is very similar in all four compounds. The P—C bond has an approximately staggered conformation, with the aniline and ethynylphenyl groups in gauche positions with respect to the P=O double bond. The two six‐membered rings are almost perpendicular. The sums of the valence angles about the N atoms vary from 344 (2) to 351 (2)°. In the crystal structures, molecules of (I), (III) and (IV) are arranged as centrosymmetric or pseudocentrosymmetric dimers connected by two N—H...O=P hydrogen bonds. The molecules of (II) are arranged as centrosymmetric dimers connected by Cmethyl—H...O=P hydrogen bonds. The N—H bond of (II) is not involved in hydrogen bonding.  相似文献   

11.
Organosoluble homopolyimides (PIs) and copolyimides (CoPIs) were synthesized from 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane (BAPP) or 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane (6FBAPP) and six kinds of commercial aromatic dianhydrides (PMDA, II a ; BTDA, II b ; BPDA, II c ; ODPA, II d ; DSDA, II e ; 6FDA, II f ). Although BAPP and II d∼f could prepare three kinds of soluble PIs ( III‐A d∼f ), likewise 6FBAPP and II c∼f could prepare four PIs ( III‐B c∼f ), the insoluble PIs were synthesized from these two diamines and other dianhydrides. However, soluble CoPIs could be prepared by alternative copolycondensation from a pair of dianhydrides of soluble PIs and insoluble PIs in certain molar ratios (m1/m2). The ratios of m1/m2 of BAPP/PMDA series CoPIs ( IV m1(d–f)/m2a ) ranged from 3–5, but ratios of 6FBAPP/PMDA series CoPIs ( V m1(c∼f)/m2a ) decreased to 2–3. The m1/m2 of the BAPP/BTDA and 6FBAPP/BTDA series CoPIs were 2, while the BAPP/BPDA series were between 1–2. Composition, solubility, tensile properties and thermal properties of these CoPIs synthesized via a two‐stage thermal cyclodehydration were determined and were compared with their corresponding PIs. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3954–3961, 2000  相似文献   

12.
Based on the bis‐triazole ligand 2, 6‐bis(1, 2,4‐triazole‐4‐yl)pyridine (L), the triazole‐iron(II) complexes [Fe(L)2(dca)2(H2O)2] · 2H2O ( 1 ) (Nadca = sodium dicyanamide), {[Fe(μ2‐L)2(H2O)2]Cl2}n ( 2 ), and {[Fe(μ2‐L)2(H2O)2](ClO4)2 · L · H2O}n ( 3 ) were isolated by solvent diffusion methods. When iron(II) salts and Nadca were used, compound 1 was isolated, which contains mononuclear Fe(L)2(dca)2(H2O)2 units. When FeCl2 or FeClO4 were used, one‐dimensional (1D) cation iron(II) chains ( 2 ) and two‐dimensional (2D) cation iron(II) networks ( 3 ) were isolated indicating anion directing structural diversity. Moreover, variable‐temperature magnetic susceptibility data of 1 – 3 were recorded in the temperature range 2–300 K. The magnetic curve of complex 2 was fitted by using the classical spin Heisenberg chain model indicating anti‐ferromagnetic interactions (J = –5.31 cm–1). Obviously complexes 1 – 3 show no detectable thermal spin crossover behaviors, the lack of spin‐crossover behavior may be correlated with FeN4O2 coordination spheres in 1 – 3 .  相似文献   

13.
The reaction of (Z)‐2‐[amino(pyridine‐2‐yl)methylene]hydrazonecarbothioamide (HAm4DH) with Mn(ClO4)2·6H2O afforded different mononuclear or polynuclear manganese(II) complexes, the nature of which apparently depended on the solvent used. For example, in ethanol a compound of formula [Mn(HAm4DH)2](ClO4)2 ( 1 ) was obtained, where HAm4DH coordinates as a common tridentate NNS donor, but the [Mn(bpy)2(NCS)2] complex ( 2 ) (bpy = 2,2'‐bipyridine) has also been obtained – probably due to C–N bond cleavage of the thiosemicarbazone. Nevertheless, in a basic aqueous medium [Mn(bpy)3](ClO4)2·0.5bpy ( 3 ) is formed and there is structural evidence for chemical transformations of the thiosemicarbazone promoted by MnII. Thus, the sulfate in {[Mn(py)4Mn(py)2(H2O)2(μ‐SO4)2]·4H2O}n ( 4 ) or sulfate and cyclooctasulfur in [Mn(pta)2(pdo)]4(SO4)2·4H2O·S8] ( 5 ), where pta is 3‐(pyridin‐2‐yl)‐1,2,4‐triazol‐5‐amine and pdo is (2R,4R/2S,4S)‐pentane‐2,4‐diolato, arise from the desulfuration and oxidation of the thiosemicarbazone ligand. The structures of complexes 2 to 5 were established by single‐crystal X‐ray diffraction. The formation of pta is the result of the oxidative cyclization of HAm4DH. In the polynuclear complex 4 , the sulfate acts as an (O,O') bridge between alternating Mn(py)2(H2O)2 and Mn(py)4 centers. In the tetranuclear complex 5 , pta acts as a bischelating ligand through the N‐pyridine and N‐triazole, and pdo act as a bridge between two manganese atoms. It is also noteworthy that in complexes 4 and 5 hydrogen bonds give rise to different self‐assembly behaviour that leads to complicated supramolecular structures.  相似文献   

14.
The one-pot hydrothermal reaction of CuCl2 with H2CPOA and 4,4'-bpy results in two new coordination polymers, [Cu(CPOA)(4,4'-bpy)(H2O)2]·1.5H2O (1) and [Cu2(HCPOA)4(4,4'-bpy)4] (2) (H2CPOA=4-carboxyphenoxy acetic acid, 4,4'-bpy=4,4'-bipyridine) since CPOA^2- anions reach equilibrium with HCPOA^- anions in the reaction system. The crystal structure of 1 shows a triple interpenetration CdSO4-like net with 1D channel, in which lattice water molecules are located. Complex 2 is a ladder-like 1D double chain structure assembled through coordination bonds and O—H…N hydrogen bonds.  相似文献   

15.
The complexes [Co(L1)(mpy)] ( 1 ), [Ni(L1)(mpy)] ( 2 ), [Co(L1)(tbpy)] · 2H2O ( 3 ), [Ni2(L1)2(tbpy)2] · 5H2O ( 4 ), [Mn2(L1)2(tbpy)2] · 3H2O ( 5 ), [Mn(L1)(biim‐3)] ( 6 ), [Ni2(L1)2(btb)2(H2O)] · 2H2O ( 7 ), [Cu(L2)(mpy)] · 7H2O ( 8 ), [Co(L2)(tbpy)(H2O)] ( 9 ), [Ni(L2)(tbpy)(H2O)] · H2O ( 10 ), [Cu(L2)(bib)] · 2H2O ( 11 ), and [Cu(L2)(btb)] · 2H2O ( 12 ) [H2L1 = (3‐carboxyl‐phenyl)‐(4‐(2′‐carboxyl‐phenyl)‐benzyl)ether, H2L2 = 3‐carboxy‐1‐(4′‐carboxybenzyl)‐2‐oxidopyridinium, mpy = 2‐(4‐(4′‐methylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), tbpy = 2‐(4‐(4′‐tert‐butylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), biim‐3 = 1,3‐bis(imidazol‐1′‐yl)propane, btb = 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene, bib = 1,4‐bis(imidazol‐1′‐ylmethyl)benzene] were synthesized. Compounds 1 – 6 have similar 1D chain structures, which are further linked by π–π interactions to generate supramolecular double chains for 1 and 2 , and supramolecular layers for 3 – 6 . Compound 7 displays a 3D 6‐connected framework with (44 · 611) topology. Compound 8 features a monomolecular structure, which is further linked by hydrogen bonds between the lattice water molecules and carboxylate oxygen atoms of L2 anions to form a 2D supramolecular layer. The monomolecular structures of 9 and 10 are connected by hydrogen bonds and π–π interactions simultaneously to generate supramolecular layers. Compounds 11 and 12 show layer structures.  相似文献   

16.
Four metal‐organic coordination polymers [Co2(L)3(nipa)2]·6H2O ( 1 ), [Cd(L)(nipa)]·3H2O ( 2 ), [Co(L) (Hoxba)2] ( 3 ) and [Ni2(L)2(oxba)2(H2O)]·1.5L·3H2O ( 4 ) were synthesized by reactions of the corresponding metal(II) salts with the rigid ligand 1,4‐bis(1H‐imidazol‐4‐yl)benzene (L) and different derivatives of 5‐nitroisophthalic acid (H2nipa) and 4,4′‐oxybis(benzoic acid) (H2oxba), respectively. The structures of the complexes were characterized by elemental analysis, FT‐IR spectroscopy and single‐crystal X‐ray diffraction. Complexes 1 and 3 have the same one‐dimensional (1D) chain while 2 is a 6‐connected twofold interpenetrating three‐dimensional (3D) network with α ‐Po 412·63 topology based on the binuclear CdII subunits. Compound 4 features a puckered two‐dimensional (2D) (4,4) network, and the large voids of the packing 2D nets have accommodated the uncoordinated L guest molecules. An abundant of N–H···O, O–H···O and C–H···O hydrogen bonding interactions exist in complexes 1–4 , which contributes to stabilize the crystal structure and extend the low‐dimensional entities into high‐dimensional frameworks. Lastly, the photoluminiscent properties of compounds 2 were also investigated.  相似文献   

17.
Two novel complexes [Cu L 2(MeOH)] ( 1 )and [Ag2 L (H L )2(MeOH)] ( 2 ) ( L = 5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐carboxylic acid) were synthesized and characterized by elemental analysis, IR and X‐ray diffraction. Complex 1 is a mononuclear structure; the molecules were assembled into an infinite 2–D supramolecular by the C–H···O weak interactions. Complex 2 is a centrosymmetric dinuclear structure with bis(unidentate) carboxylato co‐ordination mode, and the molecules were assembled into 2–D layers by C–H···O and O–H···O weak interactions.  相似文献   

18.
The zinc(II) center in the molecule of [(C23H36N4O3)ZnCl]Cl·H2O is coordinated by four nitrogen atoms of HL (1,3‐bis[2‐[2‐[(4‐methoxybenzyl) amino]ethylamino]]‐2‐propanol) and one chloro anion. The coordination moieties are connected by hydrogen bonds to form a one‐dimensional structure. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

19.
Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH2)n bridged imidazoles L(CH2)nL, n = 3–6) with chloro bridged complexes [R3P(Cl)M(μ‐Cl)M(Cl)PR3] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl2(R3P)M–L(CH2)nL–M(PR3)Cl2] 1 – 17 . The structures of [Cl2(Et3P)Pd–L(CH2)3L–Pd(PEt3)Cl2] ( 1 ), [Cl2(Bu3P)Pd–L(CH2)4L–Pd(PBu3)Cl2] ( 10 ), [Cl2(Et3P)Pd–L(CH2)5L–Pd(PEt3)Cl2] ( 3 ), [Cl2(Et3P)Pt–L(CH2)3L–Pt(PEt3)Cl2] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl2(Cp*)Ir–L(CH2)nL–Ir(Cp*)Cl2] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)2Ir(Cl)Cp*] and the methylene bridged bis(imidazoles).  相似文献   

20.
Two new CoII coordination polymers [Co4(tbip)4(bipy)4(H2O)4] ( 1 ) and [Co(tbip)(phen)(H2O)] · H2O ( 2 ) (H2tbip = 5‐tert‐butyl isophthalic acid, bipy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. Compound 1 is a tbip‐bridged tetranuclear cobalt(II) complex, which is further linked by hydrogen bonds to form a supramolecular network. Compound 2 shows a tbip‐bridged linear chain structure, which is extended by hydrogen bonds to generate a double chain. Magnetic measurements show that there are weak ferromagnetic interactions between the adjacent CoII ions in 1 .  相似文献   

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