Structures and Photoluminescence Properties of Four Cadmium(II) Coordination Polymers Synthesized by Rigid Ligands and N-Donor Ligands

2015 ◽  
Vol 68 (5) ◽  
pp. 742 ◽  
Author(s):  
Qing-Guo Meng ◽  
Lin-Tong Wang ◽  
Ji-Tao Lu ◽  
Xin Wang ◽  
Wei Lu ◽  
...  

Four metal–organic coordination polymers, [Cd2(dna)2(2,2′-bpy)2]n (1), {[Cd4(dna)4(im)3]·5H2O}n (2), {[Cd2(dna)2(4,4′-bpy)(H2O)2]·2EtOH}n (3), and {[Cd4(dna)4(1,3-dpp)4(H2O)4]·2H2O}n (4) (H2dna = 4,6-dimethyl-5-nitroisophthalic acid; 2,2′-bpy = 2,2′-bipyridine; im = imidazole; 4,4′-bpy = 4,4′-bipyridine; 1,3-dpp = 1,3-di(4-pyridyl)propane; and EtOH = ethanol, have been solvothermally synthesized and characterized. Compound 1 displays a one-dimensional (1D) ladder structure and the neighbouring ladders are further stabilized by π···π interactions to form a two-dimensional (2D) layer. Compound 2 forms a 2D layer based on infinite 1D [Cd2(COO)4]n chain and the im ligands act as terminal ligands, preventing expansion of the dimensionality. Compound 3 features a 2D 44-sql layer based on binuclear [Cd2(COO)4] secondary building units as 4-connected nodes, and is further linked to be an unusual three-dimensional (3D) supramolecular architecture by hydrogen bonds involving the coordinated water molecules, carboxylate groups, and lattice ethanol molecules. Compound 4 possesses a 2-fold interpenetrated dia net. The diverse structures and topologies of compounds 1–4 indicate that the N-containing ligands have significant effects on the formation of the final network structures. In addition, the thermal stabilities, structure comparison, and photoluminescence properties of the complexes have been investigated.

2020 ◽  
Vol 76 (8) ◽  
pp. 763-770
Author(s):  
Dong-Dong Yang ◽  
Li-Ping Lu ◽  
Miao-Li Zhu

Six two-dimensional (2D) coordination polymers (CPs), namely, poly[{μ5-3,3-[(5-carboxylato-1,3-phenylene)bis(oxy)]dibenzoato-κ6 O 1:O 1′:O 3,O 3′:O 5:O 5′}bis(N,N-dimethylformamide-κO)lanthanide(III)], [Ln(C21H11O8)(C3H7NO)2] n , with lanthanide/Ln = cerium/Ce for CP1, praseodymium/Pr for CP2, neodymium/Nd for CP3, samarium/Sm for CP4, europium/Eu for CP5 and gadolinium/Gd for CP6, have been prepared by solvothermal methods using the ligand 3,3′-[(5-carboxy-1,3-phenylene)bis(oxy)]dibenzoic acid (H3cpboda) in the presence of Ln(NO3)3. The complexes were characterized by single-crystal X-ray and powder diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis (TGA). All the structures of this family of lanthanide CPs are isomorphous with the triclinic space group P-1 and reveal that they have the same 2D network based on binuclear LnIII units, which are further extended via interlayer C—H...π interactions into a three-dimensional supramolecular structure. The carboxylate groups of the cpboda3− ligands link adjacent LnIII ions and form binuclear [Ln2(RCOO)4] secondary building units (SBUs), in which each binuclear LnIII SBU contains four carboxylate groups from different cpboda3− ligands. Moreover, with the increase of the rare-earth Ln atomic radius, the dihedral angles between the aromatic rings gradually increase. Magnetically, CP6 shows weak antiferromagnetic coupling between the GdIII ions. The solid-state luminescence properties of CP2, CP5 and CP6 were examined at ambient temperature and CP5 exhibits characteristic red emission bands derived from the Eu3+ ion (CIE 0.53, 0.31), with luminescence quantum yields of 22%. Therefore, CP5 should be regarded as a potential optical material.


2017 ◽  
Vol 73 (8) ◽  
pp. 645-651 ◽  
Author(s):  
Qiu-Ying Huang ◽  
Yang Zhao ◽  
Xiang-Ru Meng

Careful choice of the organic ligands is one of the most important parameters in the rational design and synthesis of coordination polymers. Aromatic polycarboxylates have been widely used in the preparation of metal–organic polymers since they can utilize various coordination modes to form diverse structures and can act as hydrogen-bond acceptors and donors in the assembly of supramolecular structures. Nitrogen-heterocyclic organic compounds have also been used extensively as ligands for the construction of polymers with interesting structures. In the polymers catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN 3}cobalt(II)]-μ2-benzene-1,4-dicarboxylato-κ2 O 1:O 4] dihydrate], {[Co(C8H4O4)(C12H11N4)2(H2O)2]·2H2O} n , (I), and catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN 3}nickel(II)]-μ2-benzene-1,4-dicarboxylato-κ2 O 1:O 4] dihydrate], {[Ni(C8H4O4)(C12H11N4)2(H2O)2]·2H2O} n , (II), the CoII or NiII ion lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry, coordinated by two N atoms from two imidazole rings and four O atoms from two monodentate carboxylate groups and two water molecules. The dicarboxylate ligands bridge metal ions forming a polymeric chain. The 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole ligands coordinate to the CoII or NiII centres in monodentate modes through an imidazole N atom and are pendant on opposite sides of the main chain. The two structures are isomorphous. In the crystal, the one-dimensional chains are further connected through O—H...O, O—H...N and N—H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviours and fluorescence properties of both polymers have been investigated.


2017 ◽  
Vol 73 (11) ◽  
pp. 1599-1602 ◽  
Author(s):  
Matimon Sangsawang ◽  
Kittipong Chainok ◽  
Nanthawat Wannarit

The title compound, [CdNa2(C8H4O4)2(C3H7NO)(H2O)2]nor [CdNa2(1,3-bdc)2(DMF)(H2O)2]n, is a new CdII–NaIheterobimetallic coordination polymer. The asymmetric unit consists of one CdIIatom, two NaIatoms, two 1,3-bdc ligands, two coordinated water molecules and one coordinated DMF molecule. The CdIIatom exhibits a seven-coordinate geometry, while the NaIatoms can be considered to be pentacoordinate. The metal ions and their symmetry-related equivalents are connectedviachelating–bridging carboxylate groups of the 1,3-bdc ligands to generate a three-dimensional framework. In the crystal, there are classical O—H...O hydrogen bonds involving the coordinated water molecules and the 1,3-bdc carboxylate groups and π–π stacking between the benzene rings of the 1,3-bdc ligands present within the frameworks.


2018 ◽  
Vol 74 (8) ◽  
pp. 894-900 ◽  
Author(s):  
Lin Wang ◽  
Qian-Kun Zhou ◽  
Yun Xu ◽  
Ni-Ya Li

In recent years, the design and construction of crystalline coordination complexes by the assembly of metal ions with multitopic ligands have attracted considerable attention because of the unique architectures and potential applications of these compounds. Two new coordination polymers, namely poly[[μ-trans-1-(2-aminopyridin-3-yl)-2-(pyridin-4-yl)ethene-κ2 N:N′](μ3-5-methylisophthalato-κ4 O 1,O 1′:O 3:O 3′)cadmium(II)], [Cd(C9H6O4)(C12H11N3)] n or [Cd(5-Me-ip)(2-NH2-3,4-bpe)] n , (I), and poly[[μ-trans-1-(2-aminopyridin-3-yl)-2-(pyridin-4-yl)ethene-κ2 N:N′](μ2-5-hydroxyisophthalato-κ4 O 1,O 1′:O 3:O 5)cadmium(II)], [Cd(C8H4O5)(C12H11N3)] n or [Cd(5-HO-ip)(2-NH2-3,4-bpe)] n , (II), have been prepared hydrothermally by the self-assembly of Cd(NO3)2·4H2O and trans-1-(2-aminopyridin-3-yl)-2-(pyridin-4-yl)ethene (2-NH2-3,4-bpe) with two similar dicarboxylic acids, i.e. 5-methylisophthalic acid (5-Me-H2ip) and 5-hydroxyisophthalic acid (5-HO-H2ip). The coordination network of (I) is a two-dimensional sql net parallel to (101). Adjacent sql nets are further linked to form a three-dimensional supramolecular framework via hydrogen-bonding interactions. Compound (II) is a two-dimensional (3,5)-connected coordination network parallel to (010) with the point symbol (63)(55647). As the other reactants and reaction conditions are the same, the structural differences between (I) and (II) are undoubtedly determined by the different substituent groups in the 5-position of isophthalic acid. Both (I) and (II) exhibit good thermal stabilities and photoluminescence properties.


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.


2013 ◽  
Vol 69 (9) ◽  
pp. 1022-1025 ◽  
Author(s):  
Cui-Lian Guo ◽  
Xiao-Qiang Yao ◽  
Yong-Qiang Cheng ◽  
Yan Liu

In the title compound, [Ni(C12H6O4)(C22H16N2O)2(H2O)2]n, the Ni2+cation resides on a centre of inversion in a slightly distorted octahedral [N2O4] environment. The two carboxylate groups of each naphthalene-2,6-dicarboxylate (NDC2−) ligand, which reside on centres of inversion, link the NiIIcations into a one-dimensional chain. Identical chains are linked by intermolecular hydrogen bonds between coordinated water molecules and the uncoordinated N atoms of 4-{4-[4-(pyridin-4-yl)phenoxy]phenyl}pyridine ligands to form (4,4)-topological sheets, and then the different sheets are interlocked in an inclined fashion to give a three-dimensional polycatenation network. The stability of the structure is further enhanced by π–π stacking interactions between pyridine and benzene rings.


Author(s):  
Jian-Qing Tao

In the title mixed-ligand metal–organic polymeric complex [Cd(C14H8O6S)(C16H16N2)(H2O)]n, the asymmetric unit contains a crystallographically unique CdIIatom, one doubly deprotonated 4,4′-sulfonyldibenzoic acid ligand (H2SDBA), one 3,4,7,8-tetramethyl-1,10-phenanthroline (TMPHEN) molecule and one water molecule. Each CdIIcentre is coordinated by two N atoms from the chelating TMPHEN ligand, three O atoms from monodentate carboxylate groups of three different SDBA2−ligands and one O atom from a coordinated water molecule, giving a distorted CdN2O4octahedral geometry. Single-crystal X-ray diffraction analysis reveals that the compound is a one-dimensional double-chain polymer containing 28-membered rings based on Cd2O2clusters, with a Cd...Cd separation of 3.6889 (4) Å. These chains are linked by O—H...O and C—H...O hydrogen bonds to form a three-dimensional supramolecular framework. The framework is reinforced by π–π and C—O...π interactions.


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.


2020 ◽  
Author(s):  
Phil Liebing ◽  
Florian Oehler ◽  
Juliane Witzorke ◽  
Marten Schmeide

<br>Heterobimetallic compounds of the type M’2[Pt(L)2] (L = N-dithioato-iminodiacetate, {SSC-N(CH2COO)2}3–) containing different bivalent, oxophilic metals M’ were prepared in a straightforward manner from [Pt(H2L)2] and the respective metal acetates, M’(OAc)2 (M’ = Mg–Ba, M–Cu, Cd). X-ray structure determination revealed that the products exist as zero- (Mg), one- (Mn), two- (Fe, Co, Ni, Cd), or three-dimensional (Sr) assemblies in the solid state. As a result, the water solubilities and thermal stabilities of the products cover much wider ranges than it has been seen with M’2[M(L)2] compounds having different thiophilic metal centers (M = Ni, Pd, Pt). While most of the compounds show a typical diamagnetic (Mg–Ba, Cd) or paramagnetic (Mn, Co, Ni, Cu) behaviour at ambient temperature, for Fe2[Pt(L)2] ·4 H2O an antiferromagnetic interaction of the Fe atoms is assumed. <br>


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