scholarly journals Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C2O4)3]3− Building Block

Materials ◽  
2020 ◽  
Vol 13 (23) ◽  
pp. 5341
Author(s):  
Lidija Kanižaj ◽  
Pavla Šenjug ◽  
Damir Pajić ◽  
Luka Pavić ◽  
Krešimir Molčanov ◽  
...  

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C2O4)]·1.5H2O}n (1) (bpy = 2,2’-bipyridine) and heterodimetallic {[CrCu3(bpy)3(CH3OH)(H2O)(C2O4)4][Cu(bpy)Cr(C2O4)3]·CH2Cl2·CH3OH·H2O}n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr2Cu2(phen)4(C2O4)6]·4CH3CN·2H2O}n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalato)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions were mediated by oxalate ligands in the chain [Mn(bpy)(C2O4)]n of 1, with intra-chain super-exchange interaction ? = (−3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C2O4)3]nn− (Cr2–Cu4) with alternating [Cr(C2O4)3]3− and [Cu(bpy)]2+ units mutually bridged through the oxalate group. Another chain (Cr1–Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H2O)(µ-C2O4)Cu(bpy)(CH3OH)]2+ (Cu1–Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1−Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1–Cu3 and Cr2–Cu4. A 3D polymer {[CaCr2Cu2(phen)4(C2O4)6]·4CH3CN·2H2O}n (3) comprising three different metal centers (Ca2+, Cr3+ and Cu2+) oxalate-bridged, contains Ca2+ atoms as nodes connected with four Cr3+ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (66) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [CuIICrIII], whose mutual interaction could possibly originate through the spin polarization of Ca2+ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2.

2006 ◽  
Vol 59 (9) ◽  
pp. 647 ◽  
Author(s):  
Yong-Tao Wang ◽  
Gui-Mei Tang ◽  
Da-Wei Qin

Three new inorganic–organic coordination polymers based on a versatile linking unit 2-(1H-imidazole-1-yl)acetate (Hima) and divalent Mn(ii), Ni(ii), and Cu(ii) ions, exhibiting two kinds of two dimensionalities with different topological structures, have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of MnCl2·4H2O and Ni(NO3)2·6H2O with Hima yielded neutral two-dimensional (2D) coordination polymers [M(ima)2]n, M = Mn(ii) 1, and Ni(ii) 2 with isostructural 2D coordination polymers possessing (3,6) topology structures, which further stack into three-dimensional (3D) supramolecular networks through C–H···O weak interactions. However, when Cu(NO3)2·4H2O was used, a neutral 2D coordination polymer [Cu(ima)2]n 3 consisting of rhombus units was generated, which showed a 3D supramolecular network through C–H···O weak interactions. Among these polymers, the building block ima anion exhibits different coordination modes. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal ions, plays a critical role in construction of these novel coordination polymers. Spectral and thermal properties of these new materials have also been investigated.


2019 ◽  
Vol 74 (6) ◽  
pp. 485-489
Author(s):  
Yuan Huang ◽  
Xiu-feng Yu ◽  
Zhen Rong ◽  
Yi-chun Ai ◽  
Kun Qian ◽  
...  

AbstractA new complex [Pr3NH]+ [Mn(dca)3]− · H2O (dicyanamide = dca−) was synthesized, in which the Mn2+ cations are bridged by end-to-end dca anions to form three-dimensional [Mn(dca)3]nn− networks and tripropylammonium cations reside in the cavities of these networks. The complex has been characterized by single-crystal X-ray diffraction, infrared spectroscopy, elemental analysis, and magnetic measurements. Magnetic susceptibility data indicate ferromagnetic interactions among the MnII ions.


2019 ◽  
Vol 75 (8) ◽  
pp. 1073-1083 ◽  
Author(s):  
Feng Su ◽  
Cheng-Yong Zhou ◽  
Lin-Tao Wu ◽  
Xi Wu ◽  
Jing Su ◽  
...  

Two CoII-based coordination polymers, namely poly[(μ4-biphenyl-2,2′,5,5′-tetracarboxylato){μ2-1,3-bis[(1H-imidazol-1-yl)methyl]benzene}dicobalt(II)], [Co2(C16H6O8)(C14H14N4)2] n or [Co2(o,m-bpta)(1,3-bimb)2] n (I), and poly[[aqua(μ4-biphenyl-2,2′,5,5′-tetracarboxylato){1,4-bis[(1H-imidazol-1-yl)methyl]benzene}dicobalt(II)] dihydrate], {[Co2(C16H6O8)(C14H14N4)2(H2O)2]·4H2O} n or {[Co2(o,m-bpta)(1,4-bimb)2(H2O)2]·4H2O} n (II), were synthesized from a mixture of biphenyl-2,2′,5,5′-tetracarboxylic acid, i.e. [H4(o,m-bpta)], CoCl2·6H2O and N-donor ligands under solvothermal conditions. The complexes were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction and powder X-ray diffraction analysis. The bridging (o,m-bpta)4− ligands combine with CoII ions in different μ4-coordination modes, leading to the formation of one-dimensional chains. The central CoII atoms display tetrahedral [CoN2O2] and octahedral [CoN2O4] geometries in I and II, respectively. The bis[(1H-imidazol-1-yl)methyl]benzene (bimb) ligands adopt trans or cis conformations to connect CoII ions, thus forming two three-dimensional (3D) networks. Complex I shows a (2,4)-connected 3D network with left- and right-handed helical chains constructed by (o,m-bpta)4− ligands. Complex II is a (4,4)-connected 3D novel network with ribbon-like chains formed by (o,m-bpta)4− linkers. Magnetic studies indicate an orbital contribution to the magnetic moment of I and II due to the longer Co...Co distances. An attempt has been made to fit the χM T results to the magnetic formulae for mononuclear CoII complexes, the fitting indicating the presence of weak antiferromagnetic interactions between the CoII ions.


2015 ◽  
Vol 68 (1) ◽  
pp. 121 ◽  
Author(s):  
Wenlong Liu ◽  
Xueying Wang ◽  
Mengqiang Wu ◽  
Bing Wang

Two new coordination polymers, namely, {[Cd3(bpt)2(bimb)2]·2(H2O)}n (1) and [Zn3(bpt)2(bimb)2]n (2) (bpt = biphenyl-3,4′,5-tricarboxylate, bimb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene), have been obtained under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analysis and further characterised by elemental analysis and infrared spectroscopy. Complex 1 exhibits a trinodal (4,4,4)-connected topology with Schläfli symbol of (4.62.83)4.(64.82). Complex 2 is also a three-dimensional structure and displays a (3,4,6)-connected topology with Schläfli symbol of (4.62)2.(42.66.85.102).(64.82). It is shown that the asymmetrically tricarboxylate can bear diverse structures regulated by metal ions. The photoluminescence behaviours of compounds 1 and 2 were also discussed.


2012 ◽  
Vol 67 (8) ◽  
pp. 774-782 ◽  
Author(s):  
Wei-Ting Guo ◽  
Zhi-Min Miao ◽  
Yun-Long Wang

Two chain-like coordination polymers, namely, {[Zn(saes)(4,4'-bipy)(H2O)]·H2O}n (1) and {[Cd (Hsaes)2(4,4'-bipy)(H2O)2]·2H2O}n (2), where H2saes=2-(2-hydroxybenzylideneamino)ethanesulfonic acid and 4,4'-bipy=4,4'-bipyridine, have been synthesized and characterized by singlecrystal X-ray diffraction, IR spectroscopy, elemental, thermogravimetric and photoluminescence analysis. X-Ray diffraction analyses indicate that 1and 2display octahedral metal centers with N3O3 and N2O4 donor sets, respectively. The Schiff base serves as a common N,O'-tridentate ligand in 1, and as a unique O-monodentate ligand in 2. In the crystal, both 1and 2form a 3D supramolecular architecture by O-H···O, C-H···O interactions or π···π stacking. The thermal and solid-state photoluminescence properties of both complexes have been investigated


2014 ◽  
Vol 70 (a1) ◽  
pp. C1235-C1235
Author(s):  
Robert Burrow ◽  
Giancarlo Belmonte

The proligand para-benzenediseleninic acid, (HO2SeC6H4SeO2H) (Figure), is the seleno analog to the commonly used MOF spacer proligand, terephthalic acid. Novel coordination polymers based on this proligand, and Mn(II), Fe(II), Co(II), Ni(II), Cu(II) or Zn(II) metal centers containing auxiliary water molecules, [M(O2SeC6H4SeO2)2(H2O)n], were synthesized. Depending on the reaction conditions, different pure or mixed phases can be produced. Crystal to crystal transformations of the novel coordination polymers were studied with powder X ray diffraction, infrared spectral analysis and thermal gravimetric analysis. These coordination polymers can be dehydrated with subsequent formation of new anhydrous coordination polymer phases. Some of these phases can be rehydrated to lead back to the crystalline starting materials or to new crystalline hydrated phases. We are working on the complete structural characterization of the phases.


2015 ◽  
Vol 68 (6) ◽  
pp. 956 ◽  
Author(s):  
Ming-An Dang ◽  
Zi-Feng Li ◽  
Ying Liu ◽  
Gang Li

Three coordination polymers [Sr(p-H2MOPhIDC)2]n (1) (p-H3MOPhIDC = 2-p-methoxyphenyl-1H-imidazole-4,5-dicarboxylic acid), {[Cd2(p-HMOPhIDC)2(4,4′-bipy)]⋅H2O}n (4,4′-bipy = 4,4′-bipyridine) (2), and [Zn(p-HMOPhIDC)(4,4′-bipy)]n (3) have been solvothermally synthesized, and structurally characterized by single-crystal X-ray diffraction. Polymer 1 indicates a three-dimensional framework, which can be simplified as a 6-connected lattice. Polymer 2 is also a three-dimensional framework, and contains mixed bridging ligands HMOPhIDC2– and 4,4′-bipy. Polymer 3 exhibits a sheet structure bearing infinite rectangles. The coordination modes of the p-H3MOPhIDC ligand, and the thermal and solid-state photoluminescence properties of the polymers have been investigated as well.


2019 ◽  
Vol 75 (4) ◽  
pp. 422-432 ◽  
Author(s):  
Chao Bai ◽  
Bin Liu ◽  
Huai-Ming Hu ◽  
Jin-Dian Li ◽  
Xiaofang Wang ◽  
...  

Three series of lanthanide coordination polymers, namely catena-poly[[lanthanide(III)-μ2-(benzene-1,2-dicarboxylato)-μ2-[2-(2,2′:6′,2′′-terpyridin-4′-yl)benzoato]] monohydrate], {[Ln(C8H4O4)(C22H14N3O2)]·H2O} n or {[Ln(1,2-bdc)(L)]·H2O} n , with lanthanide (Ln) = dysprosium (Dy, 1), holmium (Ho, 2) and erbium (Er, 3), poly[bis(μ2-benzene-1,3-dicarboxylato)bis[μ2-2-(2,2′:6′,2′′-terpyridin-4′-yl)benzoato]dilanthanide(III)], [Ln2(C8H4O4)2(C22H14N3O2)2] n or [Ln2(1,3-bdc)2(L)2] n , with Ln = gadolinium (Gd, 4), Ho (5) and Er (6), and poly[(μ2-benzene-1,4-dicarboxylato)[μ2-2-(2,2′:6′,2′′-terpyridin-4′-yl)benzoato]lanthanide(III)], [Ln(C8H4O4)(C22H14N3O2)] n or [Ln(1,4-bdc)(L)] n , with Ln = Dy (7), Ho (8), Er (9) and ytterbium (Yb, 10), were synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compounds 1–3 possess one-dimensional loop chains with Ln2(COO)2 units, which are extended into three-dimensional (3D) supramolecular structures by π–π interactions. Isostructural compounds 5 and 6 show 6-connected 3D networks, with pcu topology consisting of Ln2(COO)2 units. Compounds 7–10 display 8-connected 3D frameworks with the topological type rob, consisting of Ln2(COO)2 units. The influence of the coordination orientations of the aromatic dicarboxylate groups on the crystal structures is discussed.


2017 ◽  
Vol 41 (6) ◽  
pp. 365-369 ◽  
Author(s):  
Chongchong Xue ◽  
Jingwen Shi ◽  
Daopeng Zhang

The coordination polymers {Mg[Fe(L)(CN)5]}n·0.5nH2O and {MgCu2(CH3COO)6}n [L = bis( N-imidazolyl)methane] have been synthesised. X-ray diffraction revealed that {Mg[Fe(L)(CN)5]}n·0.5nH2O has a one-dimensional neutral chain structure consisting of alternating [Mg(L)2(H2O)2)]2+ species and [Fe(L)(CN)5]2– building blocks, which can be further linked into a three-dimensional supramolecular structure by inter-chain p–p interactions. {MgCu2(CH3COO)6}n has a three-dimensional network with the [MgCu2(CH3COO)6] unit as neutral core extended by Mg–O bonds. Magnetic susceptibility studies on {MgCu2(CH3COO)6}n revealed antiferromagnetic interactions between adjacent Cu(II) ions.


2018 ◽  
Vol 74 (2) ◽  
pp. 240-247 ◽  
Author(s):  
Nassima Bendjellal ◽  
Chahrazed Trifa ◽  
Sofiane Bouacida ◽  
Chaouki Boudaren ◽  
Mhamed Boudraa ◽  
...  

In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal–organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ2N,N′)bis(μ-3-phenylprop-2-enoato-κ3O,O′:O)calcium(II)], [Ca(C10H7O2)2(C10H8N2)]n, (1), and poly[(1,10-phenanthroline-κ2N,N′)(μ3-3-phenylprop-2-enoato-κ4O:O,O′:O′)(μ-3-phenylprop-2-enoato-κ3O,O′:O)barium(II)], [Ba(C10H7O2)2(C10H8N2)]n, (2), and characterized them by FT–IR and UV–Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C—H...O hydrogen bonds and π–π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297–1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.


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