Three New Isostructural Coordination Polymers with Cd(II) Clusters as the SBU: Synthesis, Structural Characterization, and Luminescence Properties (original) (raw)
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Russian Journal of Coordination Chemistry, 2019
Metal-organic 1D coordination polymers of Zn(II) and Cd(II), [{Zn(3-Bphz)(H 2 O) 4 }(3-Bphz)(NO 3) 2 ] n (I), [Zn(3-Bphz)I 2 ] n (II), [Cd(3-Bphz)I 2 ] n (III), [Cd(4-Bphz)(CH 3 COO) 2 (H 2 O)] n (IV), and [Cd(4-Bphz)(NO 3) 2 (H 2 O) 2 ] n (V), containing azines of the N,N' type, 1,2-bis(pyridin-3-ylmethylene)hydrazine (3-Bphz) and 1,2-bis(pyridin-4-ylmethylene)hydrazine (4-Bphz), as bridging ligands are synthesized. The compositions and structures of the compounds are confirmed by the data of elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray diffraction analysis (CIF files CCDC nos. 1812634-1812638 for I-V). Coordination polymers I-III have zigzag structures. The octahedral environment of the Zn 2+ ion in compound I is formed by two 3-Bphz ligands and four water molecules. The external sphere contains nitrate anions and uncoordinated 3-Bphz molecules. In isomorphous compounds II and III, the tetrahedral environment of the metal is formed by two nitrogen atoms of two bridging 3-Bphz ligands and two iodine atoms. Coordination polymers IV and V are linear. The coordination polyhedron of the Cd 2+ ion in compound IV is a pentagonal bipyramid, two vertices of which are occupied by the nitrogen atoms of two 4-Bphz molecules, and the equatorial plane is formed by two bidentate-chelating acetate anions and one water molecule. In compound V, the octahedral environment of the Сd 2+ ion is formed by two molecules of the 4-Bphz ligand, two monodentate nitrate anions, and two water molecules. All complexes are weak luminophores emitting in the blue-green spectral range.
Russian Journal of Coordination Chemistry, 2019
1,2-Benzenedicarboxylic (phthalic) acid (1,2-BdcН 2) and bipyridine ligands are used for the synthesis of the Zn(II) and Cd(II) coordination polymers. As a result, the target assembling of four complexes is carried out. The structures of the synthesized complexes are studied by X-ray diffraction analysis. Three of the obtained compounds are new coordination polymers [Zn 2 (1,2-Bdc) 2 (Bpe) 2 ] n • 0.25n(Dmf) • 0.25nH 2 O (I), [Zn 2 (1,2-Bdc) 2 (Bpp) 2 ] n (II), and [Cd(1,2-Bdc)(Bpp)(H 2 O)] n (III) (Bpe is bis(4-pyridyl)ethane, Bpp is 1,2-bis(4-pyridyl)propane, and Dmf is dimethylformamide) (CIF files CCDC nos. 1824264 (I), 1824265 (II), and 1824266 (III)), and the fourth one is the known Cd(II) compound [Cd(1,2-Bdc)(H 2 O)] n. The study of the structures of compounds I-III reveals the dimensionalities of the polymers: 3D for the Zn(II) polymer and 2D for the Cd(II) polymer. Different shapes of the coordination polyhedra of Zn(II) are found in compounds I and II, and different coordination modes of the doubly deprotonated ligand (1,2-Bdc) 2to the metals are observed in compounds I-III.
Polyhedron, 2019
A mixed ligand approach has been applied for the synthesis of a series of Zn(II) and Cd(II) coordination polymers, namely CP1 [{Zn(3-bpna)(bdc)}•CH3OH]α, CP2 [{Cd(3-bpna)(oba)}•DMF•H2O]α, CP3 [{Cd(3-bpna)(5-nipa)}•2DMF]α, CP4 [{Zn2(dpmndi)(oba)3}•4H2O]α, CP5 [{Zn(dpmndi)0.5(oba)•DMF}•DMF•H2O]α and CP6 [{Cd(dpmndi)(bdc)}•DMF]α, which are constructed by the reactions of the ligand 3-bpna or dpmndi and Zn(NO3)2•6H2O or Cd(NO3)2•4H2O in the presence of different dicarboxylate ligands, specifically terephthalic acid, 4,4'-oxydibenzoic acid and 5-nitroisophthalic acid, as a co-ligand under solvothermal conditions. These coordination polymers were structurally characterized and display 1D, 2D and 3D network structures. Moreover, their fluorescent behavior was also investigated and the results are found to be very promising.
Journal of Molecular Structure, 2018
Three new coordination polymers of {[Cd(bib) 3 ](ClO 4) 2 } n (1), [Cd(µ 2-bip) 2 (N 3) 2 ] n (2) and [Cd(µ-bib Me)Cl 2 ] n (3) were prepared by using the neutral N-donor ligands 1,4bis(imidazolyl)butane (bib), 1,3-bis(imidazolyl)propane (bip) and 1,4-bis(2methylimidazolyl)butane (bib Me) and CdX 2 (X=ClO 4-, N 3 and Cl-). The results of the X-ray measurements demonstrate that in the crystal structure of 1 and 2 the cadmium(II) ion adopts CdN 6 octahedral geometry while, in the structure of 3, the metal ion forms CdN 2 Cl 2 tetrahedral geometry. In compound 1, six bib ligands are coordinated to one central cadmium(II) to form an open 3D 2-fold interpenetrating framework of the α-polonium (pcu) type topology, while in compound 2 and 3 the N 3 or Clgroups are terminally bonded to the metal center and each linker compound (bip or bib Me) acts as bridging ligand connecting two metal ions to form a one-dimensional zigzag chain. The adjacent 1D chains of complex 2 and 3 are further extended into a non-covalent 2D network structure by C-H•••N and C-H•••Cl intermolecular hydrogen bonds, respectively. The complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction.
Polyhedron, 2013
When the ligand HH 0 L was treated with different transition metal salts at room temperature, four new isostructural coordination polymers, {[Zn(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (1), {[Cd(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (2), {[Mn(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (3), and {[Co(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (4) (HH 0 L = 2-hydroxy-5-(pyridin-4ylazo)-benzoic acid) were formed. These polymers were characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA), in addition to X-ray crystallography. X-ray single crystal studies revealed that 1-4 are 1D coordination polymers that are further extended by weak interactions to afford 3D coordination polymers. All the complexes show high thermal stability after losing coordinated and lattice solvent molecules in the temperature range 80-200°C. Upon excitation at 344 nm, complexes 1-4 exhibit solid-state luminescence at room temperature.
Crystal Growth & Design, 2013
By using isomeric N,N′-di(2-pyridyl)adipoamide (L 1), N,N′-di(3-pyridyl)adipoamide (L 2) and N,N′-di(4-pyridyl)adipoamide (L 3) and isomeric 1,2-benzenedicarboxylic acid (1,2-H 2 BDC), 1,3-benzenedicarboxylic acid (1,3-H 2 BDC) and 1,4-benzenedicarboxylic acid (1,4-H 2 BDC), eight Zn(II) and Cd(II) coordination polymers [Zn(1,2-BDC)(L 2)] ∞ , 1; [Zn 2 (1,3-BDC) 2 (L 2)(H 2 O) 2 ] ∞ , 2; [Zn 2 (1,4-B D C) 2 (L 1) (H 2 O) 2 ] ∞ , 3 ; {[Zn 2 (1 , 2-B D C) 2 (L 3)-(H 2 O) 2 ]•2H 2 O} ∞ , 4; {[Cd(1,2-BDC)(L 2)(H 2 O)]•H 2 O} ∞ , 5; [Cd 2 (1,3-BDC) 2 (L 2)(H 2 O) 4 ] ∞ , 6; {[Cd 2 (1,4-BDC) 2 (L 2) 2 ]-•(H 2 O) 3 } ∞ , 7; [Cd 2 (1,4-BDC) 2 (L 1)(H 2 O) 2 ] ∞ , 8, have been synthesized under hydrothermal conditions. Complexes 1, 4, and 5 form 1D double-looped chain, 1D chain with loops and 2D layer with loops, respectively, and complex 6 exhibits a 1D ladder chain. Complex 2 shows rare 3-fold interpenetrated hcb layers, in which each layer interdigitates with other four parallel layers by directing the 1,3-BDC ligands into the windows of the adjacent nets, whereas complexes 3 and 8 forms planar and undulated hcb layers, respectively. Complex 7 shows a 3D selfpenetrating net of {4 24 .5.6 3 }-ilc topology with a unique arrangement for the L 2 spacer ligands. The L 1 ligands in complexes 3 and 8 adopt the new tetradentate bonding mode involving chelation and bridge through two pyridyl nitrogen atoms and two amide oxygen atoms, whereas the L 2 and L 3 ligands in other complexes show the bidentate bonding mode through the two pyridyl nitrogen atoms. The various bonding modes and the ligand-isomerism of the spacer ligands BDC 2− and L 1 −L 3 as well as the identity of the metal center play important roles in determining the structural diversity.
Journal of Inorganic and Organometallic Polymers and Materials, 2013
A novel coordination polymer [Cd 2 (l-Cl) 4 (Neim) 3 ] n (1) (Neim = N-ethylimidazole) was synthesized and structurally characterized by means of elemental analysis, thermal analysis, FT-IR spectrum and singlecrystal X-ray diffraction. There are two different cadmium centers in 1. One of these metal centers has octahedral geometry, while the other has square pyramidal geometry. Two Neim ligands are coordinated to the Cd(II) ion in octahedral geometry while one Neim ligand is coordinated to the Cd(II) ion in square pyramidal geometry. Relatively weak C-HÁÁÁCl interactions between N-ethylimidazole molecules and chloro ions in the complex play an important role in the construction of a three-dimensional supramolecular framework. Complex 1 exhibits photoluminescence emission in solid state at room temperature.
Polyhedron, 2020
Four Cd(II) coordination polymers, formulated as {(H 2 betib) 2 [Cd(l-Hpdia) 2 ]ÁH 2 OÁMeOHÁdmf} n (1), {[Cd (l-Hpdia)(l-bipib)]Ádmf} n (2), [Cd(l-Hpdia)(H 2 O) 2 (l-betix) 0.5 ] n (3) and [Cd(l 3-Hpdia)(MeOH) (l-bipix) 0.5 ] n (4) (Hpdia: 5-(4-hydroxyphenylazo)isophthalate, betib or bipib: 1,4-bis(2-x-imidazol-1yl)butane, betix or bipix: 1,4-bis((2-x-imidazol-1-yl)methyl)benzene where x = ethyl-or isopropyl-) were synthesized under the same solvothermal conditions with 5-(4-hydroxyphenylazo)isophthalic acid and flexible or semi-flexible substituted bis(imidazole) linkers, and characterized by elemental analysis, IR spectroscopy, single crystal X-ray diffraction and thermal analysis methods. X-ray analysis results demonstrated that compounds 1-4 displayed 1D, 2D and 3D structures. In 1, the flexible betib ligand was protonated and the 2D structure formed by Hpdia was extended by hydrogen bonding to a 3D supramolecular network with the rtw topology. The hydrogen-bonded structure of 2 displayed a twofold 3D ? 3D interpenetrated supramolecular network with the tcj/hc topology. Compounds 3 and 4, synthesized using semi-flexible bis(imidazol) ligands, exhibited 1D and 3D frameworks, respectively. The thermal, optical and photoluminescence properties of the compounds were also investigated.
Crystal Growth & Design, 2005
The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L1) and 2,5bis(3-pyridyl)-1,3,4-oxadiazole (L2) with inorganic IIB metal salts have been investigated. Five new coordination polymers (1-5) were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Cd(L1) 2 (CH 3 CN) 2 ](ClO 4 ) 2 AE (CH 3 CN) 2 (1) crystallized in the monoclinic space group P2 1 /c, a = 8.4028 Å , b = 21.3726(13) Å , c = 10.5617(7) Å , b = 95.1200(10)°, and Z = 2. In the solid state, it adopts an infinite two-dimensional polymeric structural motif with effective cross section of ca. 14.31 · 14.31 Å . Cd(L2)(H 2 O)(NO 3 ) 2 (2) crystallized in the monoclinic space group Ia, a = 7.1203(5) Å , b = 22.2475(15) Å , c = 20.2652(16) Å , b = 90.6080(10)°, and Z = 8. In the solid state, the two Cd(II) centers are connected to each other by L2 ligands and bridging nitrates into a two-dimensional network. [ZnCl 2 (L1)] (3) and [HgI 2 (L1)] AE CH 3 CN (4) crystallized in the monoclinic crystal system (3: P2 1 /c, a = 5.3702(3) Å , b = 20.4800(11) Å , c = 12.4093(7) Å , b = 94.7930(10)°, and Z = 4; 4: P2/n, a = 17.2733(11) Å , b = 5.2173(3) Å , c = 20.4069(13) Å , b = 102.8690(10)°, and Z = 4). In the solid state, Zn(II) and Hg(II) metal centers are connected to each other by L1 ligands into a zigzag chain motif. Compound 5 (HgBr 2 (L2) is different from 3 and 4, monoclinic, P2(1)/n, a = 5.470(4) Å , b = 16.271(13) Å , c = 16.486(12) Å , b = 93.197(15)°, and Z = 4) adopts a novel one-dimensional helical chain motif which resulted from the relative different coordinated orientation of the two N-donors on L2 ligand.