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

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.

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

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229618013967 ◽

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.

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

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.807-809.2671 ◽

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.

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

Crystals ◽

10.3390/cryst10060505 ◽

2020 ◽

Vol 10 (6) ◽

pp. 505 ◽

Cited By ~ 1

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.

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

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229618001420 ◽

2018 ◽

Vol 74 (2) ◽

pp. 240-247 ◽

Cited By ~ 8

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.

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Binding sites between palladium(II) and nucleosides or nucleotides and crystal structure of [Pd(diethylenetriamine)(guanosine)](ClO4)2

Canadian Journal of Chemistry ◽

10.1139/v80-061 ◽

1980 ◽

Vol 58 (4) ◽

pp. 381-386 ◽

Cited By ~ 21

Author(s):

F. D. Rochon ◽

P. C. Kong ◽

B. Coulombe ◽

R. Melanson

Keyword(s):

Crystal Structure ◽

Binding Sites ◽

Palladium Atom ◽

X Ray Diffraction ◽

Orthorhombic Space Group ◽

X Ray ◽

R Factor ◽

Square Planar ◽

Purine Ring ◽

Coordination Plane

The interactions between [Pd(dien)Cl]Cl and some nucleosides and nucleotides were studied by nmr. The binding site of guanosine, guanosinemonophosphoric acid, xanthosine, and inosine is N(7). Cytidine is coordinated to palladium through N(3). Adenosinemonophosphate acts as a bidentate, binding two different palladium atoms at N(1) and N(7).The crystal structure of [Pd(dien)(guanosine)](ClO4)2 has been determined by X-ray diffraction. The crystals are orthorhombic, space group P212121, with a = 13.422, b = 14.587, c = 12.432, and Z = 4. The structure was refined by block-diagonal least-squares analysis to a conventional R factor of 0.047 and a weighted Rw = 0.043. The coordination around the palladium atom is square planar. Guanosine is bonded to palladium through N(7). The planar purine ring makes an angle of 63.4° with the palladium coordination plane. The structure is stabilized by hydrogen bonding.

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

Materials ◽

10.3390/ma14174871 ◽

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.

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

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229619004960 ◽

2019 ◽

Vol 75 (5) ◽

pp. 575-583 ◽

Cited By ~ 5

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.

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Effect of Hydrated Metal Salts on the Coordination Product of Cobalt(II) halide and PNP Type Ligand, 2,6-bis(di-tertbutylphosphinomethyl) pyridine

10.26434/chemrxiv.5851701 ◽

2018 ◽

Author(s):

Tasneem Siddiquee ◽

Abdul Goni

Keyword(s):

Metal Salts ◽

Molar Ratio ◽

Pincer Complexes ◽

Asymmetric Unit ◽

X Ray Diffraction ◽

Pincer Ligand ◽

Tetrahedral Geometry ◽

X Ray ◽

Distorted Tetrahedral Geometry ◽

Cobalt Center

Chemical treatment of CoX2. 6H2O (X = Cl, Br, I) with the potentially tridentate PNP pincer ligand 2,6-bis(di-tert-butylphosphinomethyl)pyridine in 1:1 molar ratio results in cobalt(II) halide-PNP pincer complexes. The effect of the hydrated metal source on molecular structure and geometry of the complexes was studied by single crystal X-ray diffraction analysis. The complexes are neutral and the cobalt center adopts a penta-coordinate system with potential atropisomerization. Within the unit cell there are two distinct molecules per asymmetric unit. One of the two phosphorus atoms in the PNP ligand was observed to be partially oxidized to phosphinoxide. Disorder in the structure reflects a mixture of square pyramidal and distorted tetrahedral geometry.

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Synthesis and Structure of a Clathrated Two-Dimensional Metal-Organic Framework: [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2·H2O (L = Bis(1-pyrazinylethylidene)hydrazine)

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20080024 ◽

2008 ◽

Vol 73 (1) ◽

pp. 24-31

Author(s):

Dayu Wu ◽

Genhua Wu ◽

Wei Huang ◽

Zhuqing Wang

Keyword(s):

Metal Organic Framework ◽

Channel Structure ◽

Two Dimensional ◽

X Ray Diffraction ◽

Guest Molecules ◽

X Ray ◽

Square Planar ◽

Metal Organic ◽

Aqueous Meoh ◽

Organic Framework

The compound [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2 was obtained by the reaction of Cd(ClO4)2, bis(1-pyrazinylethylidene)hydrazine (L) and 4,4'-bipyridine in aqueous MeOH. Single-crystal X-ray diffraction has revealed its two-dimensional metal-organic framework. The 2-D layers superpose on each other, giving a channel structure. The square planar grids consist of two pairs of shared edges with Cd(II) ion and a 4,4'-bipyridine molecule each vertex and side, respectively. The square cavity has a dimension of 11.817 × 11.781 Å. Two guest molecules of bis(1-pyrazinylethylidene)hydrazine are clathrated in every hydrophobic host cavity, being further stabilized by π-π stacking and hydrogen bonding. The results suggest that the hydrazine molecules present in the network serve as structure-directing templates in the formation of crystal structures.

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Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes

Molecules ◽

10.3390/molecules26041101 ◽

2021 ◽

Vol 26 (4) ◽

pp. 1101

Author(s):

Anirban Karmakar ◽

Anup Paul ◽

Elia Pantanetti Sabatini ◽

M. Fátima C. Guedes da Silva ◽

Armando J. L. Pombeiro

Keyword(s):

Coordination Polymer ◽

Single Crystal ◽

Coordination Polymers ◽

Metal Ion ◽

Solvent Free ◽

Lewis Acidity ◽

Carboxylate Ligand ◽

X Ray Diffraction ◽

X Ray ◽

Microwave Assisted

The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings.

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