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1.
One new two‐dimensional (2D) CuII polymer [Cu(CHDA)(H2O)]n ( 1 ) was synthesized solvothermally based on 1,1‐cyclohexanediacetic acid (H2CHDA) ligand. Single‐crystal X‐ray diffraction analysis reveals that 1 has a 2D framework structure consisting of paddle‐wheel dinuclear [Cu2] cluster unit and CHDA2– connector, which bears a 4‐connected sql network with Schläfli symbol of (44.62). Magnetic studies indicate the presence of strong antiferromagnetic coupling (J = –302 cm–1) between the two CuII ions in the paddle‐wheel dicopper(II) entity.  相似文献   

2.
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   

3.
Two coordination polymers, [Co2(Hcpip)2(phth)]n · 3n(H2O) ( 1 ) and [Mn2(Hcpip)2(phth)]n ( 2 ), {H2cpip = 2‐(2‐carboxyphenyl)imidazo[4,5‐f](1,10)‐ phenanthroline, H2phth = phthalic acid}, were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. Complex 1 is a 1D chain, in which the dinuclear [Co2(Hcpip)2]2+ units are linked through (phth)2– anions. Complex 2 is a 2D layer structure, which is constructed from the 1D chains bridged by (phth)2– anions. The magnetic properties of 1 and 2 show that the weak ferromagnetic interactions occurred between CoII ions in 1 and a weak antiferromagnetic interactions exist between MnII ions in 2 . These two complexes have good thermal stabilities.  相似文献   

4.
The coordination polymers [Cu2(tpim)2] · 2H2O ( 1 ) and [Co(H2tpim)2(MoO4)2] ( 2 ) [Htpim = 2,4,5‐tri(4‐pyridyl)‐imidazole] were synthesized. Their structures were determined by single‐crystal X‐ray diffraction and further characterized by elemental analyses, IR spectroscopy, and TG analyses. Compounds 1 and 2 both contain chiral helical‐layer structures. Compound 1 exhibits a novel 3D (3,3,4)‐connected framework with (4 · 6 · 8)(6 · 82)(4 · 6 · 83 · 10) topology, which is constructed from left‐ and right‐ helices. Compound 2 displays a 2D chiral helical‐layer structure which can be rationalized as a (3,6)‐connected 2D kgd (kagome dual) net, and these 2D layers are further extended by hydrogen‐bonding interactions to form a 3D supramolecular network. By comparing compounds 1 and 2 , it is believed that the tripodal N‐containing ligand (Htpim) plays a key role in the construction of helical coordination polymers. In addition, the photoluminescence property of compound 1 and the magnetic property of compound 2 were studied.  相似文献   

5.
Hybrid copper molybdates containing the long‐spanning bis(4‐pyridylmethyl) piperazine (bpmp) ligand were prepared via hydrothermal synthesis and structurally characterized by single‐crystal X‐ray diffraction. The reduced copper phase and major product [Cu4(MoO4)2(bpmp)4]n ( 1 ) shows 1D ribbon motifs with embedded {CuI2O2} dimeric units, built from the bpmp pillaring of [Cu4(MoO4)2] linear clusters. The oxidized copper phase and minor product {[Cu2(MoO4)2(bpmp)4] · 24H2O}n ( 2 ) displays [Cu(bpmp)2]n2n+ mutually inclined interpenetrated cationic layers cross‐pillared by molybdate tetrahedra into an unprecedented 6‐connected self‐penetrated network with 485265 topology.  相似文献   

6.
Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H22, and [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)2 complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba2+ and Cr3+. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS2N4‐octahedra with C2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO2S4‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN4‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H3O][H5O2][Cu (cyclam)]3[Cu2(1, 2‐dtsq)3]2 contains square planar [CuII(cyclam)]2+ ions and dinuclear [CuI2(1, 2‐dtsq)3]4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.  相似文献   

7.
Two new CuII coordination polymers based on α‐Keggin polyoxotungstates, [Cu2(dpa)2(H2O)2(GeW12O40)] · 0.5CH3COOH ( 1 ) and [Hdpa][Cu2(dpa)2(4,4′‐bipy)(H2O)2(PW10V2O40)] ( 2 ) (dpa = 2,2′‐dipyridylamine, 4,4′‐bipy = 4,4′‐bipyridine), were obtained by solvothermal reactions in glacial acetic acid and characterized by elemental analysis, IR spectroscopy, TG analysis, X‐ray powder diffraction, and single‐crystal X‐ray diffraction. Compound 1 exhibits a 1D two‐rowed chain constructed from [GeW12O40]4– anions coordinated with [Cu(1)(dpa)]2+ and [Cu(2)(dpa)(H2O)2]2+ fragments by four terminal oxygen atoms. Compound 2 exhibits a 2D layered structure constructed from [PW10V2O40]5– anions coordinated with [Cu(dpa)(4,4′‐bipy)0.5(H2O)]2+ fragments by four terminal oxygen atoms. Furthermore, the electrochemical properties of 1 and the photocatalytic hydrogen production of 1 and 2 were investigated.  相似文献   

8.
The 2D CuII metal‐organic framework [Cu2(bptc)(H2O)4]n · 4nH2O ( 1 ) (H4bptc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid) was hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and magnetic measurements. In the structure, bptc4– serves as a twisted Π‐shaped organic building block to connect paddlewheel [Cu2(COO)4] dinuclear units and mononuclear units through 2‐/2′‐carboxylate and 4‐/4′‐carboxylate, respectively. According to the magnetic analysis using a dimer‐plus‐monomer model, strong antiferromagnetic coupling is operative within the dinuclear unit (J = –311 cm–1 based on H = –J S 1 S 2), and the compound behaves like a mononuclear molecule at low temperature.  相似文献   

9.
The reaction of 1H‐tetrazole‐1‐acetic acid (Htza) and perchloric acid with cuprous chloride with slow evaporation at room temperature gave a novel 3D porous CuII coordination polymer, [Cu2(tza)4] · ClO4 · 4H2O ( 1 ), (tza = tetrazole‐1‐acetate). The structure exhibits an unusual 3D microporous coordination framework built up by four coordinated CuII nodes and bidentate bridging tza ligands with lvt‐type topology. Furthermore, the magnetic properties of complex 1 were also investigated.  相似文献   

10.
The title complex, [Cu(C6H4N3)]n, was synthesized by the reaction of cupric nitrate, 1H‐benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent CuI cations and two 1H‐benzotriazolate ligands. Two of the CuI cations, one with a linear two‐coordinated geometry and one with a four‐coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry. The third CuI cation, with a planar three‐coordinated geometry, is on a general position. Two CuI cations are doubly bridged by two BTA ligands to afford a noncentrosymmetric planar [Cu2(BTA)2] subunit, and two [Cu2(BTA)2] subunits are arranged in an antiparallel manner to form a centrosymmetric [Cu2(BTA)2]2 secondary building unit (SBU). The SBUs are connected in a crosswise manner via the sharing of four‐coordinated CuI cations, Cu—N bonding and bridging by two‐coordinate CuI cations, resulting in a one‐dimensional chain along the c axis. These one‐dimensional chains are further linked by C—H...π and weak van der Waals interactions to form a three‐dimensional supramolecular architecture.  相似文献   

11.
The dicyanamide‐bridged polymers with Schiff‐base ligand, [CoNaL(dca)]n ( 1 ) and [Mn2L(dca)2]n ( 2 ) [H2L = bis(3‐methoxysalicylidene)benzene‐1,2‐diamine, dca = dicyanamide] were synthesized and characterized by elemental analyses, IR spectrroscopy and single‐crystal X‐ray diffraction. The solid‐state structures reveal that polymer 1 has double dca bridged loop‐like 1D chains, in which the heterodinuclear Co2+‐Na+ units (LCoNa) are bridged by dca with coordination mode μ1,3,5. In polymer 2 , homodinuclear Mn2+‐Mn2+(LMnMn) units are linked by dca in μ1,5‐bridging mode to form 2D planes. Magnetic susceptibility studies on 2 reveals antiferromagnetic coupling interactions between the adjacent Mn2+ ions in the LMnMn unit.  相似文献   

12.
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   

13.
By employing one bridging ligand, 2,4‐pyridinedicarboxylate (2,4‐pda2?), three one‐dimensional (1D) coordination polymers of [Cu(2,4‐pda)(H2O)2] ( 1 ), {[Cu4(2,4‐pda)4(H2O)8]·3H2O} ( 2 ), and {[Cd(2,4‐pda)(H2O)3]·H2O} ( 3 ) were synthesized. A simple zigzag polymeric chain is observed for both 1 and 3 , but a railroad‐like zigzag polymeric chain is observed for 2. Almost all water molecules, whether coordinated or not, are involved in hydrogen bonding interactions and help to tie up the 1D polymeric chains of 1‐3 into a three‐dimensional (3D) network. A comparison about the coordination geometries in all similar coordination polymers available to date is also included.  相似文献   

14.
Four metal‐organic coordination polymers [Cd(4‐bpcb)1.5Cl2(H2O)] ( 1 ), [Cd(4‐bpcb)0.5(mip)(H2O)2] · 3H2O ( 2 ), [Co(4‐bpcb)(oba)(H2O)2] ( 3 ), and [Ni(4‐bpcb)(oba)(H2O)2] ( 4 ) [4‐bpcb = N,N′‐bis(4‐pyridinecarboxamide)‐1, 4‐benzene, H2mip = 5‐methylisophthalic acid, and H2oba = 4, 4′‐oxybis(benzoic acid)] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, elemental analyses, IR spectroscopy, powder X‐ray diffraction, and TG analysis. In complex 1 , two Cl anions serve as bridges to connect two Cd‐(μ1‐4‐bpcb) subunits forming a dinuclear unit, which are further linked by μ2‐bridging 4‐bpcb to generate 1D zigzag chain. Complex 2 shows a 2D 63 network constructed by [Cd‐mip]n zigzag chains and μ2‐bridging 4‐bpcb ligands. Complexes 3 and 4 are isostructural 2D (4, 4) grid networks derived from [M‐oba]n (M = Co, Ni) zigzag chains and [M‐(4‐bpcb)]n linear chains. The 1D chains for 1 and the 2D networks for 2 – 4 are finally extended into 3D supramolecular architectures by hydrogen bonding interactions. The roles of dicarboxylates and central metal ions on the assembly and structures of the target compounds were discussed. Moreover, the thermal stabilities, photoluminescent properties, and photocatalytic activities of complexes 1 – 4 and the electrochemical properties of complexes 3 and 4 were investigated.  相似文献   

15.
The reaction of the aryl‐oxide ligand H2L [H2L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO4 · 5H2O, CuCl2 · 2H2O, CuBr2, CdCl2 · 2.5H2O, and Cd(OAc)2 · 2H2O, respectively, under hydrothermal conditions gave the complexes [Cu(H2L1)2] · SO4 · 3CH3OH ( 1 ), [Cu2(H2L2)2Cl4] ( 2 ), [Cu2(H2L2)2Br4] ( 3 ), [Cd2(HL)2Cl2] ( 4 ), and [Cd2(L)2(CH3COOH)2] · H2L ( 5 ), where H2L1 [H2L1 = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H2L2 [H2L2 = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.  相似文献   

16.
Abstract. Two coordination polymers, namely, [Zn(bpe)0.5(Htbip)(tbip)0.5] · H2O ( 1 ) and [Cd(bpe)0.5(tbip)] ( 2 ) [H2tbip = 5‐tert‐butylisophthalic acid and bpe = 1, 2‐ bis(4‐pyridyl) ethane] were synthesized through hydrothermal reactions. Single‐crystal X‐ray diffraction analysis reveals that complex 1 presents a three‐dimensional (3D) six‐connected uninodal structure with the type of topology of svi‐x/I4/mcmIbam, whereas complex 2 holds a 2D 44sql layer structure. Moreover, the photoluminescent properties of the complexes at room temperature were investigated.  相似文献   

17.
Two tosylated isophthalic ligands, namely, 5‐tosyloxy‐isophthalic acid (H2toip) and 5‐tosylamino‐isophthalic acid (H2taip) were synthesized. Self‐assembly of CuII ions with H2toip and H2taip ligands under different reaction conditions (temperature, solvents, and auxiliary ligands) gave rise to three coordination polymers formulated as [Cu(toip)(py)2]n ( 1 ), [Cu6(toip)6(H2O)6]n · 8n(H2O) ( 2 ), and [Cu6(taip)6(py)4(dmf)2]n · n[(dmf)6(MeOH)2(H2O)2] ( 3 ) (py = pyridine, dmf = dimethylformamide). Compound 1 is a one‐dimensional (1D) coordination polymeric chain. Compounds 2 and 3 are two‐dimensional (2D) coordination networks featuring very similar Kagomé lattices based on the interconnection of paddle‐wheel [Cu2(COO)4] secondary building units (SBUs) and toip2–/taip2– ligands. However, the arrangement of adjacent Kagomé lattices in 2 and 3 are distinct, making them crystallize in different space groups and thereby have different crystal structures.  相似文献   

18.
Self‐assembly of the [Mo(CN)7]4– anion and the Mn2+ ion in the aqueous solution containing ammonium formate results in a new coordination polymer, {(NH4)3[(H2O)Mn3(HCOO)][Mo(CN)7]2·4H2O}n. Single crystal X‐ray analysis revealed a very complicated three‐dimensional (3D) framework, where both the [Mo(CN)7]4– and the formate anions act as bridges between the MnII centers. Magnetic measurements revealed that this compound displays ferrimagnetic ordering below 70 K. Competing antiferromagnetic interactions between the spin carriers might lead to spin frustration and non‐linear alignment of the magnetic moments. Specifically, this compound is the first mixed [Mo(CN)7]4–/HCOO bridged molecule magnet.  相似文献   

19.
In the polymeric title compound, [CuI(C10H8N4)]n, the CuI atom is in a four‐coordinated tetrahedral geometry, formed by two I atoms and two pyridine N atoms from two different 4,4′‐(diazenediyl)dipyridine (4,4′‐azpy) ligands. Two μ2‐I atoms link two CuI atoms to form a planar rhomboid [Cu2I2] cluster located on an inversion centre, where the distance between two CuI atoms is 2.7781 (15) Å and the Cu—I bond lengths are 2.6290 (13) and 2.7495 (15) Å. The bridging 4,4′‐azpy ligands connect the [Cu2I2] clusters into a two‐dimensional (2‐D) double‐layered grid‐like network [parallel to the (10) plane], with a (4,4)‐connected topology. Two 2‐D grid‐like networks interweave each other by long 4,4′‐azpy bridging ligands to form a dense 2‐D double‐layered network. To the best of our knowledge, this interwoven 2‐D→2‐D network is observed for the first time in [Cu2I2]–organic compounds.  相似文献   

20.
Three new 2D/3D supramolecular architectures derived from Cu‐organic subunits and Keggin anions, [CuII2(biz)8(HPMoVI10MoV2O40)(H2O)2] · 2H2O ( 1 ), [CuI4(biz)8(SiW12O40)] · 2H2O ( 2 ) and [CuI2(dmbiz)4(Hdmbiz)2(SiW12O40)] ( 3 ) (biz = benzimidazole, dmbiz = 5, 6‐dimethyl benzimidazole), were obtained under hydrothermal conditions. Single crystal X‐ray diffraction analysis reveals that compound 1 has two kinds of [CuII(biz)2]2+ cations, which are further extended by Keggin anions into a 2D (4, 8)‐connected supramolecular network by hydrogen bonding interactions. In compound 2 , four types of [CuI(biz)2]+ subunits link the [SiW12O40]4– anions to form a 3D (2, 6)‐connected supramolecular structure. Compound 3 shows a 3D supramolecular network with a NaCl‐type topology constructed by [CuI(dmbiz)2]+ subunits, anions, and discrete [Hdmbiz]+ cations. Moreover, the electrochemical and photocatalytic properties of compounds 1 and 2 were investigated.  相似文献   

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