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1.
Due to their versatile coordination modes and metal‐binding conformations, triazolyl ligands can provide a wide range of possibilities for the construction of supramolecular structures. Seven mononuclear transition metal complexes with different structural forms, namely aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ2N 1,N 5]zinc(II), [Zn(C14H11N4)2(H2O)], (I), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ2N 3,N 4]bis(nitrato‐κO )zinc(II), [Zn(NO3)2(C14H12N4)2], (II), bis(methanol‐κO )bis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ2N 1,N 5]zinc(II), [Zn(C14H11N4)2(CH4O)2], (III), diiodidobis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ2N 3,N 4]cadmium(II), [CdI2(C14H12N4)2], (IV), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ2N 3,N 4]bis(nitrato‐κO )cadmium(II), [Cd(NO3)2(C14H12N4)2], (V), aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ2N 1,N 5]cobalt(II), [Co(C14H11N4)2(H2O)], (VI), and diaquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ2N 1,N 5]nickel(II), [Ni(C14H11N4)2(H2O)2], (VII), have been prepared by the reaction of transition metal salts (ZnII, CdII, CoII and NiII) with 3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole (pymphtzH) under either ambient or hydrothermal conditions. These compounds have been characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. All the complexes form three‐dimensional supramolecular structures through hydrogen bonds or through π–π stacking interactions between the centroids of the pyridyl or arene rings. The pymphtzH and pymphtz entities act as bidentate coordinating ligands in each structure. Moreover, all the pyridyl N atoms are coordinated to metal atoms (Zn, Cd, Co or Ni). The N atom in the 4‐position of the triazole group is coordinated to the Zn and Cd atoms in the crystal structures of (II), (IV) and (V), while the N atom in the 1‐position of the triazolate group is coordinated to the Zn, Co and Ni atoms in (I), (III), (VI) and (VII).  相似文献   

2.
The reaction of 2‐cyanopyridine with N‐phenylthiosemicarbazide afforded 2‐[amino(pyridin‐2‐yl)methylidene]‐N‐phenylhydrazine‐1‐carbothioamide (Ham4ph) and crystals of 4‐phenyl‐5‐(pyridin‐2‐yl)‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐thione (pyph3NS, 1 , C13H10N4S). Crystals of methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl]sulfanyl}acetate (phpy2NS, 2 , C16H14N4O2S), derived from 1 , were obtained by the reaction of Ham4ph with chloroacetic acid, followed by the acid‐catalyzed esterification of the carboxylic acid with methyl alcohol. Crystals of bis(methanol‐κO)bis(methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl‐κ2N1,N5]sulfanyl}acetato)zinc(II)/cadmium(II) hexabromidocadmate(II), [Zn0.76Cd0.24(C16H14N4O2S)2(CH3OH)2][Cd2Br6] or [Zn0.76Cd0.24(phpy2NS)2(MeOH)2][Cd2Br6], 3 , and dichlorido(methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl‐κ2N1,N5]sulfanyl}acetato)mercury(II), [HgCl2(C16H14N4O2S)] or [Hg(phpy2NS)Cl2], 4 , were synthesized using ligand 2 and CdBr2 or HgCl2, respectively. The molecular and supramolecular structures of the compounds were studied by X‐ray diffractometry. The asymmetric unit of 3 is formed from CdBr3 and M(phpy2NS)(MeOH) units, where the metal centre M has a 76% occupancy of ZnII and 24% of CdII. The M2+ centre of the cation, located on a crystallographic inversion centre, is hexacoordinated and appears as a slightly distorted octahedral [MN4O2]2+ cation. The Cd centre of the anion is coordinated by two terminal bromide ligands and two bridging bromide ligands that generate [Cd2Br6]2? cadmium–bromide clusters. These clusters display crystallographic inversion symmetry forming two edge‐shared tetrahedra and serve as agents that direct the structure in the formation of supramolecular assemblies. In mononuclear complex 4 , the coordination geometry around the Hg2+ ion is distorted tetrahedral and comprises two chloride ligands and two N‐atom donors from the phpy2NS ligand, viz. one pyridine N atom and the other from triazole. In the crystal packing, all four compounds exhibit weak intermolecular interactions, which facilitate the formation of three‐dimensional architectures. Along with the noncovalent interactions, the structural diversity in the complexes can be attributed to the metal centre and to the coordination geometry, as well as to its ionic or neutral character.  相似文献   

3.
[μ‐N,N′‐Bis(pyridin‐3‐yl)benzene‐1,4‐dicarboxamide‐<!?show [forcelb]><!?tlsb=0.12pt>1:2κ2N:N′]bis{[N,N′‐bis(pyridin‐3‐yl)benzene‐1,4‐dicarboxamide‐κN]diiodidomercury(II)}, [Hg2I4(C18H14N4O2)3], is an S‐shaped dinuclear molecule, composed of two HgI2 units and three N,N′‐bis(pyridin‐3‐yl)benzene‐1,4‐dicarboxamide (L) ligands. The central L ligand is centrosymmetric and coordinated to two HgII cations via two pyridine N atoms, in a synsyn conformation. The two terminal L ligands are monodentate, with one uncoordinated pyridine N atom, and each adopts a synanti conformation. The HgI2 units show highly distorted tetrahedral (sawhorse) geometry, as the HgII centres lie only 0.34 (2) or 0.32 (2) Å from the planes defined by the I and pyridine N atoms. Supramolecular interactions, thermal stability and solid‐state luminescence properties were also measured.  相似文献   

4.
Three photoluminescent complexes containing either ZnII or CdII have been synthesized and their structures determined. Bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(dicyanamido‐κN 1)zinc(II), [Zn(C12H10N6)2(C2N3)2], (I), bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(dicyanamido‐κN 1)cadmium(II), [Cd(C12H10N6)2(C2N3)2], (II), and bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(tricyanomethanido‐κN 1)cadmium(II), [Cd(C12H10N6)2(C4N3)2], (III), all crystallize in the space group P , with the metal centres lying on centres of inversion, but neither analogues (I) and (II) nor CdII complexes (II) and (III) are isomorphous. A combination of N—H…N and C—H…N hydrogen bonds and π–π stacking interactions generates three‐dimensional framework structures in (I) and (II), and a sheet structure in (III). The photoluminescence spectra of (I)–(III) indicate that the energies of the π–π* transitions in the coordinated triazole ligand are modified by minor changes of the ligand geometry associated with coordination to the metal centres.  相似文献   

5.
A new 1,3,4‐oxadiazole‐containing bispyridyl ligand, namely 5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione (L), has been used to create the novel complexes tetranitratobis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}zinc(II), [Zn2(NO3)4(C14H12N4OS)2], (I), and catena‐poly[[[dinitratocopper(II)]‐bis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}] nitrate acetonitrile sesquisolvate dichloromethane sesquisolvate], {[Cu(NO3)(C14H12N4OS)2]NO3·1.5CH3CN·1.5CH2Cl2}n, (II). Compound (I) presents a distorted rectangular centrosymmetric Zn2L2 ring (dimensions 9.56 × 7.06 Å), where each ZnII centre lies in a {ZnN2O4} coordination environment. These binuclear zinc metallocycles are linked into a two‐dimensional network through nonclassical C—H...O hydrogen bonds. The resulting sheets lie parallel to the ac plane. Compound (II), which crystallizes as a nonmerohedral twin, is a coordination polymer with double chains of CuII centres linked by bridging L ligands, propagating parallel to the crystallographic a axis. The CuII centres adopt a distorted square‐pyramidal CuN4O coordination environment with apical O atoms. The chains in (II) are interlinked via two kinds of π–π stacking interactions along [01]. In addition, the structure of (II) contains channels parallel to the crystallographic a direction. The guest components in these channels consist of dichloromethane and acetonitrile solvent molecules and uncoordinated nitrate anions.  相似文献   

6.
Two organic–inorganic hybrid compounds have been prepared by the combination of the 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium cation with perhalometallate anions to give 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridocobaltate(II), (C12H12N2)[CoCl4], (I), and 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridozincate(II), (C12H12N2)[ZnCl4], (II). The compounds have been structurally characterized by single‐crystal X‐ray diffraction analysis, showing the formation of a three‐dimensional network through X—H...ClnM (X = C, N+; n = 1, 2; M = CoII, ZnII) hydrogen‐bonding interactions and π–π stacking interactions. The title compounds were also characterized by FT–IR spectroscopy and thermogravimetric analysis (TGA).  相似文献   

7.
The cocrystal salt tetraaquabis[trans‐1,2‐bis(pyridin‐4‐yl)ethene‐κN]iron(II) bis(1,1,3,3‐tetracyano‐2‐ethoxypropenide)–trans‐1,2‐bis(pyridin‐4‐yl)ethene (1/2), [Fe(C12H10N2)2(H2O)4](C9H5N4O)2·2C12H10N2, is a rare example of a mononuclear FeII compound with trans‐1,2‐bis(pyridin‐4‐yl)ethane (bpe) ligands. The complex cation resides on a crystallographically imposed inversion center and exhibits a tetragonally distorted octahedral coordination geometry. Both the symmetry‐independent bpe ligand and the cocrystallized bpe molecule are essentially planar. The 1,1,3,3‐tetracyano‐2‐ethoxypropenide counter‐ion is nonplanar and the bond lengths are consistant with significant electron delocalization. The extended structure exhibits an extensive O—H…N hydrogen‐bonding network with layers of complex cations joined by the cocrystallized bpe. Both the coordinated and the cocrystallized bpe are involved in π–π interactions. Hirshfeld and fingerprint plots reveal the important intermolecular interactions. Density functional theory was used to estimate the strengths of the hydrogen‐bonding and π–π interactions, and suggest that the O—H…N hydrogen bonds enhance the strength of the π‐interactions by increasing the polarization of the pyridine rings.  相似文献   

8.
Two new NiII complexes involving the ancillary ligand bis[(pyridin‐2‐yl)methyl]amine (bpma) and two different carboxylate ligands, i.e. homophthalate [hph; systematic name: 2‐(2‐carboxylatophenyl)acetate] and benzene‐1,2,4,5‐tetracarboxylate (btc), namely catena‐poly[[aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ3N,N′,N′′}nickel(II)]‐μ‐2‐(2‐carboxylatophenyl)aceteto‐κ2O:O′], [Ni(C9H6O4)(C12H13N3)(H2O)]n, and (μ‐benzene‐1,2,4,5‐tetracarboxylato‐κ4O1,O2:O4,O5)bis(aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ3N,N′,N′′}nickel(II)) bis(triaqua{bis[(pyridin‐2‐yl)methyl]amine‐κ3N,N′,N′′}nickel(II)) benzene‐1,2,4,5‐tetracarboxylate hexahydrate, [Ni2(C10H2O8)(C12H13N3)2(H2O)2]·[Ni(C12H13N3)(H2O)3]2(C10H2O8)·6H2O, (II), are presented. Compound (I) is a one‐dimensional polymer with hph acting as a bridging ligand and with the chains linked by weak C—H...O interactions. The structure of compound (II) is much more complex, with two independent NiII centres having different environments, one of them as part of centrosymmetric [Ni(bpma)(H2O)]2(btc) dinuclear complexes and the other in mononuclear [Ni(bpma)(H2O)3]2+ cations which (in a 2:1 ratio) provide charge balance for btc4− anions. A profuse hydrogen‐bonding scheme, where both coordinated and crystal water molecules play a crucial role, provides the supramolecular linkage of the different groups.  相似文献   

9.
The new 4‐amino‐1,2,4‐triazole asymmetric bridging ligand 4‐amino‐5‐(pyridin‐3‐yl)‐3‐[4‐(pyridin‐4‐yl)phenyl]‐4H‐1,2,4‐triazole (L) has been used to generate three novel isomorphic one‐dimensional coordination polymers, viz. catena‐poly[[tris[dichloridomercury(II)]‐bis{μ3‐4‐amino‐5‐(pyridin‐3‐yl)‐3‐[4‐(pyridin‐4‐yl)phenyl]‐4H‐1,2,4‐triazole}] acetonitrile monosolvate], {[Hg3Cl6(C18H14N6)2]·CH3CN}n, (I), and the bromido, {[Hg3Br6(C18H14N6)2]·CH3CN}n, (II), and iodido, {[Hg3I6(C18H14N6)2]·CH3CN}n, (III), analogs. The asymmetric ligand acts as a tridentate ligand to coordinate the three different HgII centers (two of which are symmetry‐related). Two ligands and two symmetry‐related HgII centers form centrosymmetric rectangular units which are linked into one‐dimensional chains via the other unique Hg atoms, which sit on mirror planes. The chains are elaborated into a three‐dimensional structure via interchain hydrogen bonds. The acetonitrile solvent molecules are located in ellipsoidal cavities. The luminescent character of these three coordination complexes was investigated in the solid state.  相似文献   

10.
A new 2,2′‐bi‐1H‐benzimidazole bridging organic ligand, namely 1,1′‐bis(pyridin‐4‐ylmethyl)‐2,2′‐bi‐1H‐benzimidazole, C26H20N6, L or (I), has been synthesized and used to create three new one‐dimensional coordination polymers, viz.catena‐poly[[dichloridomercury(II)]‐μ‐1,1′‐bis(pyridin‐4‐ylmethyl)‐2,2′‐bi‐1H‐benzimidazole], [HgCl2(C26H20N6)]n, (II), and the bromido, [HgBr2(C26H20N6)]n, (III), and iodido, [HgI2(C26H20N6)]n, (IV), analogues. Free ligand L crystallizes with two symmetry‐independent half‐molecules in the asymmetric unit and each L molecule resides on a crytallographic inversion centre. In structures (II)–(IV), the L ligand is also positioned on a crystallographic inversion centre, whereas the Hg centre resides on a crystallographic twofold axis. Compound (I) adopts an anti conformation in the solid state and forms a two‐dimensional network in the crystallographic bc plane viaπ–π and C—H...π interactions. The three HgII coordination complexes, (II)–(IV), have one‐dimensional zigzag chains composed of L and HgX2 (X = Cl, Br and I), and the HgII centres are in a distorted tetrahedral [HgX2N2] coordination geometry. Complexes (III) and (IV) are isomorphous, whereas complex (II) displays an interesting conformational difference from the others, i.e. a twist in the flexible bridging ligand.  相似文献   

11.
By the solvothermal reaction under acidic conditions of Cu(NO3)2·3H2O, Na2C2O4 and the N,N′‐ditopic organic coligands 1‐(pyridin‐4‐yl)piperazine (ppz) and 1,2‐bis(pyridin‐4‐yl)ethane (bpa), two novel anionic copper(II) coordination compounds were obtained, namely the one‐dimensional coordination polymer catena‐poly[4‐(pyridin‐1‐ium‐4‐yl)piperazin‐1‐ium [[(oxalato‐κ2O1,O2)copper(II)]‐μ‐oxalato‐κ3O1,O2:O1′]], {(C9H15N3)[Cu(C2O4)2)]}n or {(H2ppz)[Cu(C2O4)2]}n, (I), and the discrete ionic complex 4,4′‐(ethane‐1,2‐diyl)dipyridinium bis(oxalato‐κ2O1,O2)copper(II), (C12H14N2)[Cu(C2O4)2] or (H2bpa)[Cu(C2O4)2], (II). The products were characterized by single‐crystal X‐ray diffraction, elemental analysis, powder X‐ray diffraction, thermogravimetric analyses and UV and IR spectroscopic techniques. The [Cu(C2O4)2]2− units for (I) and (II) are stabilized by H2ppz2+ and H2bpa2+ cations, respectively, via charge‐assisted hydrogen bonds. Also, a study of the pH‐controlled synthesis of this system shows that (I) was obtained at pH values of 2–4. When using bpa, a two‐dimensional square‐grid network of [Cu(C2O4)(bpa)]n was obtained at a pH of 4. This indicates that the pH of the reaction also plays a key role in the structural assembly and coordination abilities of oxalate and N,N′‐ditopic coligands.  相似文献   

12.
In the crystals of the five title compounds, tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(ethanol‐O)dicopper(II)–ethanol (1/2), [Cu2(C6H11O2)4(C2H6O)2]·2C2H6O, (I), tetrakis(μ‐3,3‐dimethylbutyrato‐O:O′)bis(2‐methylpyridine‐N)di­copper(II), [Cu2(C6H11O2)4(C6H7N)2], (II), tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(3‐methylpyridine‐N)di‐copper(II), [Cu2(C6H11O2)4(C6H7N)2], (III), tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(4‐methylpyridine‐N)di‐copper(II), [Cu2(C6H11O2)4(C6H7N)2], (IV), and tetrakis‐(μ‐3,3‐dimethylbutyrato‐O:O′)bis(3,3‐dimethylbutyric acid‐O)dicopper(II), [Cu2(C6H11O2)4(C6H12O2)2], (V), the di­nuclear CuII complexes all have centrosymmetric cage structures and (IV) has two independent molecules. The Cu?Cu separations are: (I) 2.602 (3) Å, (II) 2.666 (3) Å, (III) 2.640 (2) Å, (IV) 2.638 (4) Å and (V) 2.599 (1) Å.  相似文献   

13.
The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the CuI and CuII oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C15H17N3)]·0.18H2O, (1), catena‐poly[[copper(I)‐μ2‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ5N,N′,N′′:C2,C3] perchlorate acetonitrile monosolvate], {[Cu(C15H17N3)]ClO4·CH3CN}n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) perchlorate, [CuCl(C15H17N3)]ClO4, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu2Cl2(C15H17N3)2][(C6H5)4B]2, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two CuI complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the CuI atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with CuII show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu2Cl2 moiety.  相似文献   

14.
The design and synthesis of metal–organic frameworks (MOFs) have attracted much interest due to the intriguing diversity of their architectures and topologies. However, building MOFs with different topological structures from the same ligand is still a challenge. Using 3‐nitro‐4‐(pyridin‐4‐yl)benzoic acid (HL) as a new ligand, three novel MOFs, namely poly[[(N,N‐dimethylformamide‐κO)bis[μ2‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ3O,O′:N]cadmium(II)] N,N‐dimethylformamide monosolvate methanol monosolvate], {[Cd(C12H7N2O4)2(C3H7NO)]·C3H7NO·CH3OH}n, ( 1 ), poly[[(μ2‐acetato‐κ2O:O′)[μ3‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ3O:O′:N]bis[μ3‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ4O,O′:O′:N]dicadmium(II)] N,N‐dimethylacetamide disolvate monohydrate], {[Cd2(C12H7N2O4)3(CH3CO2)]·2C4H9NO·H2O}n, ( 2 ), and catena‐poly[[[diaquanickel(II)]‐bis[μ2‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ2O:N]] N,N‐dimethylacetamide disolvate], {[Ni(C12H7N2O4)2(H2O)2]·2C4H9NO}n, ( 3 ), have been prepared. Single‐crystal structure analysis shows that the CdII atom in MOF ( 1 ) has a distorted pentagonal bipyramidal [CdN2O5] coordination geometry. The [CdN2O5] units as 4‐connected nodes are interconnected by L? ligands to form a fourfold interpenetrating three‐dimensional (3D) framework with a dia topology. In MOF ( 2 ), there are two crystallographically different CdII ions showing a distorted pentagonal bipyramidal [CdNO6] and a distorted octahedral [CdN2O4] coordination geometry, respectively. Two CdII ions are connected by three carboxylate groups to form a binuclear [Cd2(COO)3] cluster. Each binuclear cluster as a 6‐connected node is further linked by acetate groups and L? ligands to produce a non‐interpenetrating 3D framework with a pcu topology. MOF ( 3 ) contains two crystallographically distinct NiII ions on special positions. Each NiII ion adopts an elongated octahedral [NiN2O4] geometry. Each NiII ion as a 4‐connected node is linked by L? ligands to generate a two‐dimensional network with an sql topology, which is further stabilized by two types of intermolecular OW—HW…O hydrogen bonds to form a 3D supramolecular framework. MOFs ( 1 )–( 3 ) were also characterized by powder X‐ray diffraction, IR spectroscopy and thermogravimetic analysis. Furthermore, the solid‐state photoluminescence of HL and MOFs ( 1 ) and ( 2 ) have been investigated. The photoluminescence of MOFs ( 1 ) and ( 2 ) are enhanced and red‐shifted with respect to free HL. The gas adsorption investigation of MOF ( 2 ) indicates a good separation selectivity (71) of CO2/N2 at 273 K (i.e. the amount of CO2 adsorption is 71 times higher than N2 at the same pressure).  相似文献   

15.
In poly[aqua(μ3‐benzene‐1,4‐dicarboxylato‐κ5O1,O1′:O1:O4,O4′)[2‐(pyridin‐3‐yl‐κN)‐1H‐benzimidazole]cadmium(II)], [Cd(C8H4O4)(C12H9N3)(H2O)]n, (I), each CdII ion is seven‐coordinated by the pyridine N atom from a 2‐(pyridin‐3‐yl)benzimidazole (3‐PyBIm) ligand, five O atoms from three benzene‐1,4‐dicarboxylate (1,4‐bdc) ligands and one O atom from a coordinated water molecule. The complex forms an extended two‐dimensional carboxylate layer structure, which is further extended into a three‐dimensional network by hydrogen‐bonding interactions. In catena‐poly[[diaquabis[2‐(pyridin‐3‐yl‐κN)‐1H‐benzimidazole]cobalt(II)]‐μ2‐benzene‐1,4‐dicarboxylato‐κ2O1:O4], [Co(C8H4O4)(C12H9N3)2(H2O)2]n, (II), each CoII ion is six‐coordinated by two pyridine N atoms from two 3‐PyBIm ligands, two O atoms from two 1,4‐bdc ligands and two O atoms from two coordinated water molecules. The complex forms a one‐dimensional chain‐like coordination polymer and is further assembled by hydrogen‐bonding interactions to form a three‐dimensional network.  相似文献   

16.
1‐[6‐(1H‐Pyrrolo[2,3‐b]pyridin‐1‐yl)pyridin‐2‐yl]‐1H‐pyrrolo[2,3‐b]pyridin‐7‐ium tetrachloridoferrate(III), (C19H14N5)[FeCl4], (II), and [2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl‐κN7)pyridine‐κN]bis(nitrato‐κO)copper(II), [Cu(NO3)2(C19H13N5)], (III), were prepared by self‐assembly from FeCl3·6H2O or Cu(NO3)2·3H2O and 2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl)pyridine [commonly called 2,6‐bis(azaindole)pyridine, bap], C19H13N5, (I). Compound (I) crystallizes with Z′ = 2 in the P space group, with both independent molecules adopting a transtrans conformation. Compound (II) is a salt complex with weak C—H...Cl interactions giving rise to a zigzag network with π‐stacking down the a axis. Complex (III) lies across a twofold rotation axis in the C2/c space group. The CuII center in (III) has an N3O2 trigonal–bipyramidal environment. The nitrate ligand coordinates in a monodentate fashion, while the bap ligand adopts a twisted tridentate binding mode. C—H...O interactions give rise to a ribbon motif.  相似文献   

17.
Three isotypic rare earth complexes, catena‐poly[[aquabis(but‐2‐enoato‐κ2O,O′)yttrium(III)]‐bis(μ‐but‐2‐enoato)‐κ3O,O′:O3O:O,O′‐[aquabis(but‐2‐enoato‐κ2O,O′)yttrium(III)]‐μ‐4,4′‐(ethane‐1,2‐diyl)dipyridine‐κ2N:N′], [Y2(C4H5O2)6(C12H12N2)(H2O)2], the gadolinium(III) analogue, [Gd2(C4H5O2)6(C12H12N2)(H2O)2], and the gadolinium(III) analogue with a 4,4′‐(ethene‐1,2‐diyl)dipyridine bridging ligand, [Gd2(C4H5O2)6(C12H10N2)(H2O)2], are one‐dimensional coordination polymers made up of centrosymmetric dinuclear [M(but‐2‐enoato)3(H2O)]2 units (M = rare earth), further bridged by centrosymmetric 4,4′‐(ethane‐1,2‐diyl)dipyridine or 4,4′‐(ethene‐1,2‐diyl)dipyridine spacers into sets of chains parallel to the [20] direction. There are intra‐chain and inter‐chain hydrogen bonds in the structures, the former providing cohesion of the linear arrays and the latter promoting the formation of broad planes parallel to (010).  相似文献   

18.
Polypyridyl multidentate ligands based on ethylenediamine backbones are important metal‐binding agents with applications in biomimetics and homogeneous catalysis. The seemingly hexadentate tpena ligand [systematic name: N,N,N′‐tris(pyridin‐2‐ylmethyl)ethylenediamine‐N′‐acetate] reacts with zinc chloride and zinc bromide to form trichlorido[μ‐N,N,N′‐tris(pyridin‐2‐ylmethyl)ethylenediamine‐N′‐acetato]dizinc(II), [Zn2(C22H24N5O2)Cl3], and tribromido[μ‐N,N,N′‐tris(pyridin‐2‐ylmethyl)ethylenediamine‐N′‐acetato]dizinc(II), [Zn2Br3(C22H24N5O2)]. One ZnII ion shows the anticipated N5O coordination in an irregular six‐coordinate site and is linked by an anti carboxylate bridge to a tetrahedral ZnX3 (X = Cl or Br) unit. In contrast, the CuII ions in aquatribromido[μ‐N,N,N′‐tris(pyridin‐2‐ylmethyl)ethylenediamine‐N′‐acetato]dicopper(II)–tribromido[μ‐N,N,N′‐tris(pyridin‐2‐ylmethyl)ethylenediamine‐N′‐acetato]dicopper(II)–water (1/1/6.5) [Cu2Br3(C22H24N5O2)][Cu2Br3(C22H24N5O2)(H2O)]·6.5H2O, occupy two tpena‐chelated sites, one a trigonal bipyramidal N3Cl2 site and the other a square‐planar N2OCl site. In all three cases, electrospray ionization mass spectra were dominated by a misleading ion assignable to [M(tpena)]+ (M = Zn2+ and Cu2+).  相似文献   

19.
The complex poly[[aqua(μ2‐phthalato‐κ2O1:O2){μ3‐2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetato‐κ4N2,N3:O:O′}{μ2‐2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetato‐κ3N2,N3:O}dizinc(II)] dihydrate], {[Zn2(C10H8N3O2)2(C8H4O4)(H2O)]·2H2O}n, has been prepared by solvothermal reaction of 2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetonitrile (PPAN) with zinc(II). Under hydrothermal conditions, PPAN is hydrolyzed to 2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetate (PPAA). The structure determination reveals that the complex is a one‐dimensional double chain containing cationic [Zn4(PPAA)4]4+ structural units, which are further extended by bridging phthalate ligands. The one‐dimensional chains are extended into a three‐dimensional supramolecular architecture via hydrogen‐bonding and π–π stacking interactions.  相似文献   

20.
Assemblies of pyrazine‐2,3‐dicarboxylic acid and CdII in the presence of bis(1,2,4‐triazol‐1‐yl)butane or bis(1,2,4‐triazol‐1‐yl)ethane under ambient conditions yielded two new coordination polymers, namely poly[[tetraaqua[μ2‐1,4‐bis(1,2,4‐triazol‐1‐yl)butane‐κ2N4:N4′]bis(μ2‐pyrazine‐2,3‐dicarboxylato‐κ3N1,O2:O3)dicadmium(II)] dihydrate], {[Cd2(C6H2N2O4)2(C8H12N6)(H2O)4]·2H2O}n, (I), and poly[[diaqua[μ2‐1,2‐bis(1,2,4‐triazol‐1‐yl)ethane‐κ2N4:N4′]bis(μ3‐pyrazine‐2,3‐dicarboxylato‐κ4N1,O2:O3:O3′)dicadmium(II)] dihydrate], {[Cd2(C6H2N2O4)2(C6H8N6)(H2O)2]·2H2O}n, (II). Complex (I) displays an interesting two‐dimensional wave‐like structure and forms a distinct extended three‐dimensional supramolecular structure with the help of O—H...N and O—H...O hydrogen bonds. Complex (II) has a three‐dimensional framework structure in which hydrogen bonds of the O—H...N and O—H...O types are found.  相似文献   

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