scholarly journals Zn/Ni and Zn/Pd Heterobimetallic Coordination Polymers with [SSC-N(CH2COO)2]3− Ligands

Crystals ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 505 ◽  
Author(s):  
Phil Liebing ◽  
Florian Oehler ◽  
Juliane Witzorke
Keyword(s):  
Coordination Polymers ◽  
Thermal Analyses ◽  
X Ray Diffraction ◽  
Sequential Approach ◽  
X Ray ◽  
Ir And Nmr Spectroscopy ◽  
Carboxylate Groups ◽  
Polymeric Chains ◽  
Polymeric Structures ◽  
Mode A

In the construction of heterobimetallic coordination polymers based on dithiocarbamato–carboxylate (DTCC ligands), platinum as a thiophilic metal center can be replaced by the cheaper nickel or palladium. The compounds Zn[Pd(HL)2] and Zn2[M(L)2] (M = Ni, Pd; L = {SSC-N(CH2COO)2}3−) were prepared in a sequential approach starting from K3(L). The products were characterized by IR and NMR spectroscopy, thermal analyses, and single-crystal X-ray diffraction. The products decompose under nitrogen between 300 and 400 °C. Zn[Pd(HL)2] · 6H2O forms polymeric chains in the solid state, and the Zn2[M(L)2] · 14H2O (M = Ni, Pd) exhibit two-dimensional polymeric structures, each being isotypic with the respective Zn/Pt analogs. While the carboxylate groups in all these products are coordinated to zinc in a κO-monodentate mode, a structural variant of Zn2[Ni(L)2] having κO:κO′-briding carboxylate groups was also obtained. Exchange of the metal sites in the two Ni/Zn compounds was not observed, and these compounds are therefore diamagnetic.

A new twofold interpenetrated two-dimensional cadmium(II) coordination polymer constructed from 2,2′-(benzene-1,4-dicarboxamido)dipropionate

2018 ◽  
Vol 74 (11) ◽  
pp. 1434-1439
Author(s):  
Hong-Tao Zhang ◽  
Xiao-Long Wang
Keyword(s):  
Coordination Polymer ◽  
Coordination Polymers ◽  
Self Assembly ◽  
Fluorescence Emission ◽  
Functional Materials ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylate Groups ◽  
Potential Applications

In recent years, much initial interest and enthusiasm has focused on the self-assembly of coordination polymers due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. As part of an exploration of chiral coordination polymers, a new twofold interpenetrated two-dimensional (2D) coordination polymer, namely, poly[[tetraaquabis[μ3-(2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionato-κ5 O,O′:O′′,O′′′:O′′]dicadmium(II)] trihydrate], {[Cd2(C14H14N2O6)2(H2O)4]·3H2O} n , has been synthesized by the reaction of Cd(CH3COO)2·2H2O with the designed ligand (2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionic acid (H2 L). The compound has been structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis. In the crystal structure, each CdII cation binds to three carboxylate groups from two crystallographically independent L 2− dianions. Four carboxylate groups link two crystallographically independent cadmium cations into a 4,4-connected secondary building unit (SBU). The resulting SBUs are extended into a two-dimensional folding sheet via the terephthalamide moiety of the ligand as a spacer, which can be simplified as a (4,4)-connected 4,4L15 net with the point symbol (3.53.62)(32.52.62). In the lattice, two independent folding sheets interpenetrate each other to yield a double-sheet layer. The resulting 2D layers pack in parallel arrays through intermolecular hydrogen bonds and interlayer π–π interactions. The thermal stability and photoluminescence properties of the title compound have been investigated and it exhibits an enhanced fluorescence emission and a longer lifetime compared with free H2 L.

The Syntheses and Structures of Two New Zn(II) Complexes Based on 3-Nitrobenzoato Ligand

2013 ◽  
Vol 807-809 ◽  
pp. 2671-2674
Author(s):  
Ying Bing Lu ◽  
Fang Mei Jian ◽  
Shuang Jin
Keyword(s):  
Single Crystal ◽  
Coordination Polymers ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Face To Face ◽  
Π Interactions ◽  
Carboxylate Groups ◽  
Supramolecular Chain ◽  
Supramolecular Layer

Two new Zn (II) coordination polymers with 3-nitrobenzoato ligands have been prepared, and their structures have been characterized by single-crystal X-ray diffraction techniques. The structure of [Zn (3-nbz)2(μ-4,4'-bpy)]n(1) (3-nbz = 3-nitrobenzoato, 4,4'-bpy = 4,4'-bipyridine) shows 1-D chains originating from terminal 3-nbz ligands andμ-4,4'-bpy molecules. The chains are further connected through face-to-face π stacking interactions to genenate a 2-D supramolecular layer. In Zn (3-nbz)2(2,2'-bpy) (2) (2,2'-bpy = 2,2'-bipyridine), carboxylate groups exhibit chelated bidentate to give discrete mononuclear units, which are linked by face-to-face π-π and C-H···π interactions to produce a 1-D supramolecular chain.

scholarly journals Synthesis and Structure of novel Luminescent lanthanide organic frameworks.

2014 ◽  
Vol 70 (a1) ◽  
pp. C1259-C1259
Author(s):  
Mohammed S. M. Abdelbaky ◽  
Zakariae Amghouz ◽  
Santiago Granda
Keyword(s):  
Thermal Analyses ◽  
Luminescence Properties ◽  
X Ray Diffraction ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Carboxylate Groups ◽  
Transmission Electron ◽  
Scanning Transmission ◽  
Conventional Electrode ◽  
Li Ion

Lanthanide-Organic frameworks (LnOFs) are currently attracting increasing attention due to their excellent luminescence properties, in which both Ln3+ and organic linkers can be used to give rise to luminescence materials with increased brightness and emission quantum yield [1,2]. Lithium doped MOFs are of particular interest due to the recent studies showing enhanced H2 uptake, as well as promising candidates for replacing the conventional electrode in Li-ion batteries [3,4]. Herein, novel Lithium-lanthanide frameworks based on a rigid dicarboxylic acid, formulated as [LiLn(BDC)2(H2O)·2(H2O)] (Ln = Y, Dy, Ho, Er, Yb, Y1-xEux, Y1-xTbx and H2BDC = Terephthalic acid), have been obtained as single phases under hydrothermal conditions. The crystal structures were solved by single-crystal X-ray diffraction and the bulk characterized by powder X-ray diffraction (PXRD), thermal analyses (TG-MS and DSC), vibrational spectroscopy (FTIR), scanning/transmission electron microscopy (SEM-EDX, TEM, SAED, STEM-EDX), and powder X-ray thermodiffractometry (HT-XRD). All compounds are isostructural (monoclinic P21/c, a = 11.6365(7) Å, b =16.0920(2) Å, c = 13.2243(8) Å and β = 132.23(1)° for Ln = Y [5]) and possess a 3D framework with 1D trigonal channels running along the [101] direction contain water molecules. The structure is built up of unusual four-membered rings formed by edge- and vertex-shared {LnO8} and {LiO4} polyhedra. The four-membered rings are isolated and connected to each other via carboxylate groups. Topologically, the 3D frameworks belongs to a new 2-nodal 3,10-c net with point symbol of {4.5^2}2{4^14.5^10.6^18.7.8^2}. HT-XRD reveals that the compounds undergo phase transformation upon dehydration process which is a reversible process involving a spontaneous rehydration characterized by fast kinetic. The luminescence properties of selected compounds are also studied.

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.

Cooperative metal–ligand influence on the formation of coordination polymers, and conducting and photophysical properties of Tl(i) β-oxodithioester complexes

2018 ◽  
Vol 47 (45) ◽  
pp. 16264-16278 ◽  
Author(s):  
Chote Lal Yadav ◽  
Gunjan Rajput ◽  
Krishna K. Manar ◽  
Kavita Kumari ◽  
Michael G. B. Drew ◽  
...  
Keyword(s):  
Single Crystal ◽  
Coordination Polymers ◽  
Photophysical Properties ◽  
X Ray Diffraction ◽  
X Ray ◽  
Polymeric Structures ◽  
Metal Ligand

Eight novel luminescent and semiconducting Tl(i) β-oxodithioester complexes forming 1D/2D coordination polymeric structures were investigated using single crystal X-ray diffraction.

scholarly journals Investigating the geometrical preferences of a flexible benzimidazolone-based linker in the synthesis of coordination polymers

2017 ◽  
Vol 4 (12) ◽  
pp. 171064 ◽  
Author(s):  
Corey L. Jones ◽  
Elizabeth A. Marsden ◽  
Adam C. Nevin ◽  
Benson M. Kariuki ◽  
Mohan M. Bhadbhade ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Binding Sites ◽  
Metal Salts ◽  
Diacetic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylate Groups ◽  
Square Planar ◽  
Transition Metal Salts ◽  
Group 2

A series of new group 2 coordination polymers, MgL  ={MgL(H 2 O)(DMF) 0.75 } ∞ , CaL  = {CaL(DMF) 2 } ∞ , SrL  = {SrL(H 2 O) 0.5 } ∞ and BaL  = {BaL(H 2 O) 0.5 } ∞ , were synthesized using a flexible benzimidazolone diacetic acid linker ( H 2 L ) in which the two carboxylic acid binding sites are connected to a planar core via {–CH 2 –} spacers that can freely rotate in solution. In a ‘curiosity-led' diversion from group 2 metals, the first row transition metal salts Mn 2+ , Cu 2+ and Zn 2+ were also reacted with L to yield crystals of MnL = {MnL(DMF)(H 2 O) 3.33 } ∞ , Cu 3 L 2  = {Cu 3 L 2 (DMF) 2 (CHO 2 ) 2 } ∞ and ZnL  = {ZnL(DMF)} ∞ . Crystal structures were obtained for all seven materials. All structures form as two-dimensional sheets and contain six-coordinate centres, with the exception of ZnL, which displays tetrahedrally coordinated metal centres, and Cu 3 L 2 , which contains square planar coordinated metal centres and Cu paddle-wheels. In each structure, the linker adopts one of two distinct conformations, with the carboxylate groups either cis or trans with respect to the planar core. All materials were also characterized by powder X-ray diffraction and thermogravimetric analysis.

Syntheses, supramolecular networks and Hirshfeld surface and thermal analyses of two new cadmium chloride coordination polymers with an N,O-chelating ligand

2019 ◽  
Vol 75 (2) ◽  
pp. 120-127 ◽  
Author(s):  
Rafika Bouchene ◽  
Sofiane Bouacida
Keyword(s):  
Coordination Polymers ◽  
Noncovalent Interactions ◽  
Thermal Analyses ◽  
Topological Analysis ◽  
Three Dimensional ◽  
Bidentate Ligand ◽  
Hirshfeld Surface ◽  
X Ray Diffraction ◽  
X Ray ◽  
Supramolecular Networks

Two new coordination polymers, namely poly[[(3-aminopyrazin-4-ium-2-carboxylate-κ2 N 1,O)di-μ-chlorido-cadmium(II)] monohydrate], {[CdCl2(C5H5N3O2)]·H2O} n , (1), and poly[2-amino-3-carboxypyrazin-1-ium [(3-aminopyrazine-2-carboxylato-κ2 N 1,O)di-μ-chlorido-cadmium(II)] monohydrate], {(C5H6N3O2)[Cd(C5H4N3O2)Cl2]·H2O} n , (2), have been synthesized from the reaction of cadmium(II) chloride and 3-aminopyrazine-2-carboxylic acid (Hapca) under mild conditions in acidic media. The two coordination polymers have been characterized by single-crystal X-ray diffraction and show chloride-bridged zigzag chains with octahedrally coordinated metal ions, where Hapca acts as a bidentate ligand via the π-conjugated N atom and a carboxylate O atom. The chains are further interconnected via noncovalent interactions into three-dimensional supramolecular networks. The dominant H...O and H...Cl interactions for both compounds were quantified using Hirshfeld surface analysis. The thermal stability and topological analysis of the two-dimensional networks of (1) and (2) are also discussed.

scholarly journals New Coordination Polymers of Selected Lanthanides with 1,2-Phenylenediacetate Linker: Structures, Thermal and Luminescence Properties

Materials ◽  
2021 ◽  
Vol 14 (17) ◽  
pp. 4871
Author(s):  
Renata Łyszczek ◽  
Iwona Rusinek ◽  
Agnieszka Ostasz ◽  
Justyna Sienkiewicz-Gromiuk ◽  
Dmytro Vlasyuk ◽  
...  
Keyword(s):  
Single Crystal ◽  
Coordination Polymers ◽  
Structural Similarity ◽  
Spectroscopic Properties ◽  
Luminescence Spectroscopy ◽  
X Ray Diffraction ◽  
Metal Centers ◽  
X Ray ◽  
Gaseous Products ◽  
Carboxylate Groups

Solvothermal reactions of lanthanide (III) salts with 1,2-phenylenediacetic acid in N,N′-dimethylformamide (DMF) solvent lead to the formation of the metal complexes of the general formula Ln2(1,2-pda)3(DMF)2, where Ln(III) = Pr(1), Sm(2), Eu(3), Tb(4), Dy(5), and Er(6), 1,2-pda = [C6H4(CH2COO)2]2−. The compounds were characterized by elemental analysis, powder and single-crystal X-ray diffraction methods, thermal analysis methods (TG-DSC and TG-FTIR), infrared and luminescence spectroscopy. They exhibit structural similarity in the two groups (Pr, Sm, and Eu; Tb, Dy, and Er), which was reflected in their thermal behaviours and spectroscopic properties. Single-crystal X-ray diffraction studies reveal that Sm(2) and Eu(3) complexes form 2D coordination polymers with four crystallographically independent metal centers. Every second lanthanide ion is additionally coordinated by two DMF molecules. The 1,2-phenylenediacetate linker shows different denticity being: penta- and hexadentate while carboxylate groups exhibit bidentate-bridging, bidentate-chelating, and three-dentate bridging-chelating modes. The infrared spectra reflect divergence between these two groups of complexes. The complexes of lighter lanthanides contain in the structure coordinated DMF molecules, while in the structures of heavier complexes, DMF molecules appear in the inner and outer coordination sphere. Both carboxylate groups are deprotonated and engaged in the coordination of metal centers but in different ways in such groups of complexes. In the groups, the thermal decomposition of the isostructural complexes occurs similarly. Pyrolysis of complexes takes place with the formation of such gaseous products as DMF, carbon oxides, ortho-xylene, ethers, water, carboxylic acids, and esters. The complexes of Eu and Tb exhibit characteristic luminescence in the VIS region, while the erbium complex emits NIR wavelength.

Cadmium(II) three-dimensional coordination polymers constructed from 1,3,5-tris(4-carboxyphenoxy)benzene: synthesis, crystal structure, fluorescence and I2 sorption characterization

2019 ◽  
Vol 75 (5) ◽  
pp. 575-583 ◽  
Author(s):  
Yuting Bai ◽  
Meirong Han ◽  
Enxi Wu ◽  
Sisi Feng ◽  
Miaoli Zhu
Keyword(s):  
Coordination Polymers ◽  
Coordination Mode ◽  
3D Structure ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylate Groups ◽  
3D Network ◽  
3D Framework ◽  
Point Symbol

Two three-dimensional (3D) CdII coordination polymers, namely poly[[di-μ-aqua-diaquabis{μ5-4,4′,4′′-[benzene-1,3,5-triyltris(oxy)]tribenzoato}tricadmium(II)] dihydrate], {[Cd3(C27H15O9)2(H2O)4]·2H2O} n , (I), and poly[[aqua{μ6-4,4′,4′′-[benzene-1,3,5-triyltris(oxy)]tribenzoato}(μ-formato)[μ-1,1′-(1,4-phenylene)bis(1H-imidazole)]dicadmium(II)] dihydrate], {[Cd2(C27H15O9)(C12H10N4)(HCOO)(H2O)]·2H2O} n , (II), have been hydrothermally synthesized from the reaction system containing Cd(NO3)2·4H2O and the flexible tripodal ligand 1,3,5-tris(4-carboxyphenoxy)benzene (H3tcpb) via tuning of the auxiliary ligand. Both complexes have been characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra, powder X-ray diffraction and thermogravimetric analysis. Complex (I) is a 3D framework constructed from trinuclear structural units and tcpb3− ligands in a μ5-coordination mode. The central CdII atom of the trinuclear unit is located on a crystallographic inversion centre and adopts an octahedral geometry. The metal atoms are bridged by four syn–syn carboxylate groups and two μ2-water molecules to form trinuclear [Cd3(COO)4(μ2-H2O)2] secondary building units (SBUs). These SBUs are incorporated into clusters by bridging carboxylate groups to produce pillars along the c axis. The one-dimensional inorganic pillars are connected by tcpb3− linkers in a μ5-coordination mode, thus forming a 3D network; its topology corresponds to the point symbol (42.62.82)(44.62)2(45.66.84)2. In contrast to (I), complex (II) is characterized by a 3D framework based on dinuclear cadmium SBUs, i.e. [Cd2(COO)3]. The two symmetry-independent CdII ions display different coordinated geometries, namely octahedral [CdN2O4] and monocapped octahedral [CdO7]. The dinuclear SBUs are incorporated into clusters by bridging formate groups to produce pillars along the c axis. These pillars are further bridged either by tcpb3− ligands into sheets or by 1,4-bis(imidazol-1-yl)benzene ligands into undulating layers, and finally these two-dimensional surfaces interweave, forming a 3D structure with the point symbol (4.62)(47.614). Compound (II) exhibits reversible I2 uptake of 56.8 mg g−1 with apparent changes in the visible colour and the UV–Vis and fluorescence spectra, and therefore may be regarded as a potential reagent for the capture and release of I2.

Axially Chiral Bis(α-amino Acid)s and Their Deamino Analogues. Synthesis and Configurational Assignment

1998 ◽  
Vol 63 (2) ◽  
pp. 211-221 ◽  
Author(s):  
Miloš Tichý ◽  
Luděk Ridvan ◽  
Miloš Buděšínský ◽  
Jiří Závada ◽  
Jaroslav Podlaha ◽  
...  
Keyword(s):  
Amino Acid ◽  
Nmr Spectra ◽  
Building Blocks ◽  
X Ray Diffraction ◽  
Amino Groups ◽  
X Ray ◽  
Configurational Assignment ◽  
Symmetry Properties ◽  
Axially Chiral ◽  
Polymeric Structures

The axially chiral bis(α-amino acid)s cis-2 and trans-2 as possible building blocks for polymeric structures of novel type of helicity were prepared. Their configuration has been determined by NMR spectroscopy and, in the case of the trans-isomer, confirmed by single-crystal X-ray diffraction. Analogous pair of stereoisomeric diacids cis-3 and trans-3, devoid of the amino groups, was also prepared and their configuration assigned. The observed differences in the NMR spectra of cis- and trans-isomers of 2 and 3 are discussed from the viewpoint of their different symmetry properties.

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