A new family of lanthanide coordination polymers based on 3,3′-[(5-carboxylato-1,3-phenylene)bis(oxy)]dibenzoate: synthesis, crystal structures and magnetic and luminescence properties

2020 ◽  
Vol 76 (8) ◽  
pp. 763-770
Author(s):  
Dong-Dong Yang ◽  
Li-Ping Lu ◽  
Miao-Li Zhu
Keyword(s):  
Coordination Polymers ◽  
Three Dimensional ◽  
Atomic Radius ◽  
Luminescence Properties ◽  
Antiferromagnetic Coupling ◽  
Quantum Yields ◽  
New Family ◽  
Carboxylate Groups ◽  
Secondary Building Units ◽  
Solvothermal Methods

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.

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 ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Three Dimensional ◽  
Photoluminescence Properties ◽  
Thermal Stabilities ◽  
Structure Comparison ◽  
Layer Compound ◽  
Carboxylate Groups ◽  
Secondary Building Units ◽  
Coordinated Water ◽  
Dna 2

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.

Syntheses, structures and characterization of isomorphous CoII and NiII coordination polymers based on 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole and benzene-1,4-dicarboxylate

2017 ◽  
Vol 73 (8) ◽  
pp. 645-651 ◽  
Author(s):  
Qiu-Ying Huang ◽  
Yang Zhao ◽  
Xiang-Ru Meng
Keyword(s):  
Coordination Polymers ◽  
Rational Design ◽  
Three Dimensional ◽  
Spectroscopic Properties ◽  
Polymeric Chain ◽  
Design And Synthesis ◽  
Carboxylate Groups ◽  
Metal Organic ◽  
The One ◽  
Ir Spectroscopic

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.

Bright near Infrared Neodymium Emission from Europium Sensitisation in β-Triketonate Coordination Polymers

2018 ◽  
Author(s):  
Laura Abad Galán ◽  
Alexandre Sobolev ◽  
Brian Skelton ◽  
Eli Zysman-Colman ◽  
Mark Ogden ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Near Infrared ◽  
Photophysical Properties ◽  
Luminescence Properties ◽  
Quantum Yields ◽  
High Quantum

Isomorphous <i>β</i>-triketonate-based lanthanoid polymers containing tris(4-methylbenzoyl)methane (<b>mtbm</b>) and RbOH with formula, {[Ln(Rb)(<b>mtbm</b>)<sub>4</sub>]<sub>2</sub>}<i><sub>n </sub></i>(Ln = Eu<sup>3+ </sup>and Nd<sup>3+</sup>) have been synthesised and structurally characterised. The photophysical properties for the Nd<sup>3+</sup> complex presented long lifetimes and relatively high quantum yields in comparison with analogous <i><u>β</u></i>-diketonate complexes. Mixed lanthanoid complexes were also formed and their luminescence properties studied, with effective sensitisation of the <sup>4</sup>F<sub>3/2 </sub>of<sub> </sub> Nd<sup>3+ </sup>via the <sup>5</sup>D<sub>0 </sub>of Eu<sup>3+</sup>, which is to the best of our knowledge the first example of Eu<sup>3+</sup> to Nd<sup>3+</sup> sensitisation in coordination polymers <br>

Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties

2018 ◽  
Vol 74 (2) ◽  
pp. 240-247 ◽  
Author(s):  
Nassima Bendjellal ◽  
Chahrazed Trifa ◽  
Sofiane Bouacida ◽  
Chaouki Boudaren ◽  
Mhamed Boudraa ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Coordination Polymers ◽  
Crystal Engineering ◽  
Alkaline Earth ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Carboxylate Groups ◽  
A Chain

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.

Synthesis and structural characterization of two coordination polymers constructed by bis(4-(1H-imidazol-1-yl)phenyl)methanone and 5-(tert-butyl)isophthalate ligands

2019 ◽  
Vol 74 (3) ◽  
pp. 261-265 ◽  
Author(s):  
Gao-Feng Wang ◽  
Shu-Wen Sun ◽  
Wei-Bing Wang ◽  
Hong Sun ◽  
Shao-Fei Song
Keyword(s):  
Single Crystal ◽  
Coordination Polymers ◽  
Weak Interactions ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Dimensional Network ◽  
Elemental Analyses ◽  
Solvothermal Methods

AbstractTwo coordination polymers, {[Co(bipmo)(tbip)]·3H2O}n (1) and {[Cd(bipmo)(tbip)]·3H2O}n (2) (bipmo=bis(4-(1H-imidazol-1-yl)phenyl)methanone, H2tbip=5-tert-butylisophthalic acid), were synthesized by solvothermal methods and structurally characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction. The results from single-crystal X-ray diffraction data indicate that the solid state structures of 1 and 2 consist of metal-aromatic carboxylate layers, which are pillared by weak interactions to generate a three-dimensional network. The topological structures of 1 and 2 are uninodal nets based on 3-connected nodes with the Schläfli symbol of {63}.

scholarly journals Energy Transfer Between Eu3+ and Nd3+ in Near-Infrared Emitting β-Triketonate Coordination Polymers

2018 ◽  
Author(s):  
Laura Abad Galán ◽  
Alexandre Sobolev ◽  
Brian Skelton ◽  
Eli Zysman-Colman ◽  
Mark Ogden ◽  
...  
Keyword(s):  
Energy Transfer ◽  
Coordination Polymers ◽  
Near Infrared ◽  
Photophysical Properties ◽  
Coordination Complex ◽  
Luminescence Properties ◽  
Quantum Yields ◽  
High Quantum

Isomorphous<i>β</i>-triketonate-based lanthanoid polymers containing tris(4-methylbenzoyl)methanide (<b>mtbm</b>) and Rb<sup>+</sup>with formula,{[Ln(Rb)(<b>mtbm</b>)<sub>4</sub>]<sub>2</sub>}<i><sub>n </sub></i>(Ln = Eu<sup>3+ </sup>and Nd<sup>3+</sup>) have been synthesised and structurally characterised. The photophysical properties for the Nd<sup>3+</sup>complex presented long lifetimes and relatively high quantum yields in comparison with analogous <i><u>β</u></i>-diketonate complexes. Mixed lanthanoid complexes were also formed and their luminescence properties studied, with effective sensitisation of the <sup>4</sup>F<sub>3/2 </sub>of<sub></sub> Nd<sup>3+ </sup>via the <sup>5</sup>D<sub>0 </sub>of Eu<sup>3+</sup>, which is to the best of our knowledge the first example of Eu<sup>3+</sup>to Nd<sup>3+</sup>sensitisation in a coordination complex or polymer.<br>

Neue Koordinationspolymere auf der Basis der Naphthalin-1,4,5,8- tetracarboxylat-hydrate von Ca, Sr und Ba / New Coordination Polymers Based on Naphthalene-1,4,5,8-tetracarboxylate Hydrates of Ca, Sr, and Ba

2006 ◽  
Vol 61 (11) ◽  
pp. 1383-1390 ◽  
Author(s):  
Irena Senkovska
Keyword(s):  
Aqueous Solution ◽  
Oxygen Atom ◽  
Coordination Polymers ◽  
Three Dimensional ◽  
Chain Structure ◽  
Coordination Network ◽  
Carboxylate Groups ◽  
Layer Structures ◽  
A Chain ◽  
Oxygen Atoms

Crystals of [Ca(NTC)(H2O)2]·H2O (1) (NTC = naphthalene-1,4,5,8-tetracarboxylate-1,8-monoanhydride) and [Sr2(NTC)2(H2O)8]·H2O (3) were obtained by layering an aqueous solution of sodium naphthalene-1,4,5,8-tetracarboxylate with an aqueous solution of CaCl2 or SrCl2, respectively. Crystals of [Sr(NTC)(H2O)2]·2H2O (2) and [Ba(NTC)(H2O)2] (4) were obtained by gel crystallisation. The NTC in 1 and 2 is tridentate, and in 4 pentadentate, forming bonds to the cations using the oxygen atoms of the carboxylate and one oxygen atom of anhydride groups. In 3 the cations are associated only via the oxygen atoms of carboxylate groups. 1 and 2 have layer structures, 3 has a chain structure, and 4 forms a three-dimensional coordination network. The number of O atoms around the cations is eight for 1, 2 and 4, and nine for 3.

Structural diversity, magnetic properties and luminescence of NiII, CoII and ZnII coordination polymers derived from 3,3′-[(5-carboxy-1,3-phenylene)bis(oxy)]dibenzoic acid and 1,10-phenanthroline

2019 ◽  
Vol 75 (12) ◽  
pp. 1580-1592 ◽  
Author(s):  
Dong-Dong Yang ◽  
Li-Ping Lu ◽  
Miao-Li Zhu
Keyword(s):  
Coordination Polymers ◽  
Structural Diversity ◽  
Complex Iii ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Carboxylate Groups ◽  
Distorted Octahedral ◽  
Secondary Building Units ◽  
Ft Ir ◽  
Ferromagnetic Interactions

Three novel coordination polymers (CPs), namely poly[[di-μ-aqua-bis{μ4-3,3′-[(5-carboxylato-1,3-phenylene)bis(oxy)]dibenzoato-κ5 O 1:O 1′,O 3:O 5:O 5′}bis(1,10-phenanthroline-κ2 N,N′)trinickel(II)] dimethylformamide 1.5-solvate trihydrate], {[Ni3(C21H11O8)2(C12H8N2)2(H2O)2]·1.5C3H7NO·3H2O} n , (I), poly[[di-μ-aqua-bis{μ4-3,3′-[(5-carboxylato-1,3-phenylene)bis(oxy)]dibenzoato-κ5 O 1:O 1′,O 3:O 5:O 5′}bis(1,10-phenanthroline-κ2 N,N′)tricobalt(II)] diethylamine disolvate tetrahydrate], {[Co3(C21H11O8)2(C12H8N2)2(H2O)2]·2C2H7N·4H2O} n , (II), and catena-poly[[aqua(1,10-phenanthroline-κ2 N,N′)zinc(II)]-μ-5-(3-carboxyphenoxy)-3,3′-oxydibenzoato-κ2 O 1:O 3], [Zn(C21H12O8)(C12H8N2)(H2O)] n , (III), have been synthesized by the reaction of different metal ions (Ni2+, Co2+ and Zn2+), 3,3′-[(5-carboxy-1,3-phenylbis(oxy)]dibenzoic acid (H3cpboda) and 1,10-phenanthroline (phen) under solvothermal conditions. All the CPs were characterized by elemental analysis, single-crystal and powder X-ray diffraction, FT–IR spectroscopy and thermogravimetric analysis. Complexes (I) and (II) have isomorphous structures, featuring similar linear trinuclear structural units, in which the central NiII/CoII atom is located on an inversion centre with a slightly distorted octahedral [NiO6]/[CoO6] geometry. This comprises four carboxylate O-atom donors from two cpboda3− ligands and two O-atom donors from bridging water molecules. The terminal NiII/CoII groups are each connected to the central NiII/CoII cation through two μ1,3-carboxylate groups from two cpboda3− ligands and one water bridge, giving rise to linear trinuclear [M 3(μ2-H2O)2(RCOO)4] (M = Ni2+/Co2+) secondary building units (SBUs) and the SBUs develop two-dimensional-networks parallel to the (100) plane via cpboda3− ligands with new (32·4)2(32·83·9)2(34·42.82·94·103) topological structures. Zinc complex (III) displays one-dimensional coordination chains and the five-coordinated Zn atom forms a distorted square-pyramidal [ZnO3N2] geometry, which is completed by two carboxylate O-atom donors from two distinct Hcpboda2− ligands, one O atom from H2O and two N atoms from a chelating phen ligand. Magnetically, CP (I) shows weak ferromagnetic interactions involving the carboxylate groups, and bridging water molecules between the nickel(II) ions, and CP (II) shows antiferromagnetic interactions between the Co2+ ions. The solid-state luminescence properties of CP (III) were examined at ambient temperature and the luminescence sensing of Cr2O7 2−/CrO4 2− anions in aqueous solution for (III) has also been investigated.

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