Grid Coordination Polymer Research Articles

Coordination-Driven Heterochiral Self-Assembly: Construction of Cd(II) Coordination Polymers with Sorption Behaviors for Iodine and Dyes.

A racemic bispyridyl ligand (L) was synthesized via a Schiff base condensation reaction. Four Cd(II) complexes, {[CdL2Cl2]·2DMF}n (1), [CdLI2]n (2), {[CdL2Br2]·4H2O}n (3), and {[CdL2(H2O)2](NO3)2·2CH3OH·8H2O}n (4), were synthesized and further characterized based on this ligand. Single-crystal structures show that the coordination-driven assembly of the bispyridyl ligand with Cd(II) salts bearing different counteranions can lead to multidimensional coordination polymers via a heterochiral self-discrimination process. Complex 1 exists as a one-dimensional (1D) looped chain polymer, and complex 2 exists as a 1D zigzag chain polymer. Complex 3 is a 2D grid coordination polymer, and complex 4 exists as a 3D framework polymer. Furthermore, the iodine sorption capacities of the four complexes were investigated in the solution of n-hexane and water as well as in the iodine steam. The dye sorption behaviors were investigated in water, which showed that complex 2 exhibited good adsorption for crystal violet (CV), while complex 4 had good adsorption capability toward direct yellow 4 (DY).

Crystal structure and photocatalytic degradation properties of a new two-dimensional zinc coordination polymer based on 4,4ʹ-oxy-bis(benzoic acid)

Abstract A new two-dimensional ZnII coordination framework [Zn(1,3-BMIB) (OBA)] n (1) (where H2OBA is 4,4ʹ-oxy-bis(benzoic acid) and 1,3-BMIB is 1,3-bis(2-methyl-1-imidazolyl)benzene) has been prepared and characterized through IR spectroscopy, elemental and thermal analysis, and single-crystal X-ray diffraction. Complex 1 is a (4, 4) grid coordination polymer with a layer structure. It exhibits high photocatalytic degradation effects upon UV irradiation of methylene blue and methylene orange aqueous solutions.

Front Cover: One‐Dimensional Looped Chain and Two‐Dimensional Square Grid Coordination Polymers: Encapsulation of Bis(1,2,4‐Triazole)‐ trans ‐cyclohexane into the Voids (Eur. J. Inorg. Chem. 5/2019)

Front Cover: One‐Dimensional Looped Chain and Two‐Dimensional Square Grid Coordination Polymers: Encapsulation of Bis(1,2,4‐Triazole)‐ <i>trans</i> ‐cyclohexane into the Voids (Eur. J. Inorg. Chem. 5/2019)

One‐Dimensional Looped Chain and Two‐Dimensional Square Grid Coordination Polymers: Encapsulation of Bis(1,2,4‐Triazole)‐trans‐cyclohexane into the Voids

AbstractInvited for the cover of this issue are Yann Garcia from Université catholique de Louvain, Belgium, and collaborators from partner universities and research centers. The cover image shows the square grid shape of an unprecedented CuII coordination polymer with an “ancient temple architecture”.

One‐Dimensional Looped Chain and Two‐Dimensional Square Grid Coordination Polymers: Encapsulation of Bis(1,2,4‐Triazole)‐trans‐cyclohexane into the Voids

Two new coordination polymers [Cu(btzx)2(MeOH)2](NO3)2 (1) and [Cu(btrcy)2(H2O)2](ClO4)2·btrcy (2) have been synthesized by reacting two bis‐triazole/tetrazole‐ligands namely m‐xylylene‐bis(tetrazole) (btzx) and bis(1,2,4‐triazole)‐trans‐cyclohexane (btrcy) with Cu(NO3)2 and Cu(ClO4)2 respectively in a 1:3 metal/ligand ratio. These compounds are shown to form X‐ray quality single‐crystals under different conditions, and the crystal structures have been determined by single‐crystal X‐ray diffraction (SXRD). The SXRD data analysis revealed that 1 and 2 are 1D looped chain and 2D‐square grid coordination polymers, respectively. More interestingly, the 2D‐square grid architecture in 2 acts as an excellent host for the large guest ligand molecule btrcy, which is encapsulated within the voids of the 2D coordination polymer.

A new two-dimensional CdII coordination polymer based on 1,3-bis(2-methyl-1H-imidazol-1-yl)benzene and 1,3-phenylenediacetic acid: synthesis, crystal structure and physical properties.

A novel two-dimensional CdII coordination framework, poly[[[μ-1,3-bis(2-methyl-1H-imidazol-1-yl)benzene-κ2N:N'](μ-1,3-phenylenediacetato-κ4O,O':O'',O''')cadmium(II)] dihydrate], {[Cd(C10H8O4)(C14H14N4)]·2H2O}n or {[Cd(PDA)(1,3-BMIB)]·2H2O}n [1,3-BMIB is 1,3-bis(2-methyl-1H-imidazol-1-yl)benzene and H2PDA is 1,3-phenylenediacetic acid], has been prepared and characterized using IR, elemental analysis, thermal analysis and single-crystal X-ray diffraction, the latter revealing that the compound is a (4,4) grid coordination polymer with layers oriented parallel to the bc crystal planes. In the crystal, adjacent layers are further connected by O-H...O and C-H...O hydrogen bonds, forming a three-dimensional structure in the solid state. In addition, the compound exhibits strong fluorescence emissions and shows photocatalytic activity for the degradation of methylene blue in the solid state at room temperature.

Nitroaromatic-detecting zinc and cadmium coordination polymers with methyl-substituted aliphatic dicarboxylate and 4,4′-dipyridylamine ligands and diverse topologies

Hydrothermal reaction of a metal nitrate, a methyl-substituted aliphatic dicarboxylic acid, and the hydrogen-bonding capable 4,4′-dipyridylamine (dpa) ligand afforded four crystalline coordination polymers whose dimensionality, topology, and interpenetration scheme depends on the aliphatic tether length, methyl group position, and coordination geometry at the metal. The four new phases were structurally characterized via single-crystal X-ray diffraction. [Zn(22dmg)(dpa)]n (1, 22dmg = 2,2-dimethylglutarate) displays a system of mutually inclined interpenetrated (4,4) grid coordination polymer layers. [Zn(33dmg)(dpa)]n (2, 33dmg = 3,3-dimethylglutarate), in contrast to 1, displays a stacked arrangement of pairs of (4,4) grid coordination polymer layers, without any interpenetration. [Zn(3mad)(dpa)]n (3, 3mad = 3-methyladipate) possesses a system of four-fold interpenetrated 66dia topology coordination polymer networks. [Cd(33dmg)(dpa)]n (4) displays a 2-fold interpenetrated 41263pcu 3D topology, based on pillaring of dimer-based [Cd2(33dmg)2]n layers by pairs of dpa ligands. Luminescent behavior in 1–4 is attributed to intra-ligand molecular orbital transitions within the dpa aromatic pyridyl rings. The new phases were also surveyed for the ability to detect nitroaromatics in ethanol suspension, with 4 providing optimum response for nitrobenzene detection. Thermal decomposition behavior is also discussed herein.

Nitrobenzene-detecting 2D and 3D cadmium phenylenediamine coordination polymers with N,N′-ethylenediaminebis(isonicotinamide) auxiliary ligands

Hydrothermal reaction of cadmium nitrate, either 1,2-phenylenediacetic acid (12phdaH2) or 1,3-phenylenediacetic acid (13phdaH2), and the long-spanning dipyridylamide ligand N,N′-ethylenediaminebis(isonicotinamide) (ebin) produced a pair of new coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd(12phda)(ebin)(H2O)]·H2O}n (1) exhibits 2D non-interpenetrated (4,4) grid coordination polymer layers stacked in an alternating ABAB pattern. In contrast, {[Cd(13phda)(ebin)(H2O)]·H2O}n (2) exhibits a very uncommon 3D 4-fold interpenetrated 658 cds topology. Compounds 1 and 2 showed potential as detectors for nitrobenzene in ethanol suspension, with more efficacious adsorption by the layered phase 1. Thermal properties of both new materials were also investigated.

Divergent topologies in divalent metal furandicarboxylate or thiophenedicarboxylate coordination polymers with bis(4-pyridylformyl)piperazine coligands

Hydrothermal reaction of a metal nitrate, 2,5-furandicarboxylic acid (H2fdc), and the long-spanning dipyridylamide ligand bis(4-pyridylformyl)piperazine (bpfp) produced three coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd2(fdc)2(bpfp)(H2O)4]·10H2O}n (1) possesses 1D 3-connected coordination polymer ladders co-crystallized with decameric water molecule clusters. {[Cu(fdc)(bpfp)(H2O)2]·2H2O}n (2) exhibits (4,4) grid coordination polymer layers stacked in an unusual parallel ABCD pattern. {[Ni(fdc)(bpfp)(H2O)2]·4H2O}n (3) also manifests (4,4) grid coordination polymer layers, but these engage in 2D+2D→3D mutually inclined interpenetration. Hydrothermal reaction of metal nitrates, 2,5-thiophenedicarboxylic acid (H2tdc), bpfp afforded {[Zn(tdc)(bpfp)(H2O)]·2H2O}n (4), {[Cd(tdc)(bpfp)(H2O)]·2H2O}n (5), {[Ni2(tdc)2(bpfp)2(H2O)4]·3H2O}n (6), and {[Cu(tdc)(bpfp)(H2O)2]·3H2O}n (7). Compounds 4 and 5 exhibit (4,4) sawtooth coordination polymer layer motifs that engage in relatively uncommon 2D+2D→3D parallel interpenetration. Compounds 6 and 7 both showed 2D+2D→3D mutually inclined interpenetration of parallel sets of (4,4) grid layer motifs, but with different orientations of the heterocycles within their respective metal/tdc chain submotifs. Thermal properties of all new materials were also investigated. The luminescent cadmium and zinc derivatives 1, 4, and 5 were assayed as potential detectors for nitrobenzene in methanol suspension.

Metal-dependent dimensionality in divalent metal coordination polymers containing diphenate and bis(4-pyridylformyl)piperazine ligands

Hydrothermal synthesis has afforded a pair of paramagnetic divalent metal diphenate coordination polymers containing long-spanning bis(4-pyridylformyl)piperazine (4-bpfp) ligands. Single-crystal X-ray diffraction revealed an important structure directing role on the part of the metal coordination environment. [Cu(diphenate)(4-bpfp)]n (1, diphenate=biphenyl-2,2′-dicarboxylate) shows a system of 2-fold parallel interpenetrated (4,4) grid coordination polymer layers. {[Co(diphenate)(4-bpfp)]·2H2O}n (2) possesses anti-syn bridged {Co(OCO)2}n infinite 1-D chains, linked into a non-interpenetrated 66 3-D diamondoid net. A variable temperature magnetic susceptibility study of 2 indicates the presence of weak ferromagnetic coupling, concomitant with single-ion effects. Thermal properties of these materials are also discussed.

ChemInform Abstract: Square Grid and Pillared Square Grid Coordination Polymers ‐ Fertile Ground for Crystal Engineering of Structure and Function

AbstractReview: 95 refs.

Varied Layer Topologies in Luminescent Zinc Coordination Polymers with Flexible Aromatic ortho‐Dicarboxylate and Dipyridyl Ligands

AbstractHydrothermal synthesis has afforded four divalent zinc flexible‐arm aromatic ortho‐dicarboxylate coordination polymers containing dipyridyl coligands. According to X‐ray crystallography, all four show layered coordination polymer structures. Nevertheless there is significant ligand influence on the nature of zinc atom aggregation and overall topology. In both {[Zn2(hmph)2(dpa)2]·2H2O}n (1) (hmph = homophthalate, dpa = 4, 4′‐dipyridylamine), and {[Zn2(hmph)2(dpe)2](ClO4)2·H2dpe·4H2O}n (2) [dpe = bis(4‐pyridyl)ethane], large {Zn2(hmph)2} dimeric units are evident, along with an overall herringbone (6, 3) layer topology. The longer span of the dpe ligands results in larger incipient channels, which can accommodate protonated dpe dications and perchlorate counterions. In {[Zn2(hmph)2(3‐pna)]·H2O}n (3) (3‐pna = 3‐pyridylnicotinamide), {Zn2(OCO)2} anti‐syn bridged dimers and {Zn2(OCO)4} syn‐syn paddlewheel dimers coexist and are linked together by hmph and 3‐pna ligands into decorated (4, 4) grid coordination polymer layers. {[Zn(1, 2‐phda)(3‐pina)]·2H2O}n (4) (1, 2‐phda = 1, 2‐phenylenediacetate, 3‐pina = 3‐pyridylisonicotinamide) manifests an undulating (4, 4) grid structure with isolated zinc atoms; the “wavelength” of the layers measures over 40 Å. Luminescent properties of these materials are also reported.

Square Grid and Pillared Square Grid Coordination Polymers – Fertile Ground for Crystal Engineering of Structure and Function

Square grid coordination polymers (CPs) based upon four-connected metal centres linked by linear bifunctional ligands such as 4,4'-bipyridine were first reported in 1990 and the study of their pillared variants began in 1995. It was quickly realized by crystal engineers that the modularity of such CPs creates families of related compounds or platforms which in turn affords opportunities for systematic study of structure/function relationships in the context of catalysis, magnetism and porosity. This review covers the historical development of this important class of CPs before addressing recent studies of variants which incorporate 4,4'-bipyridine and related linkers to facilitate control over pore size and inorganic anion pillars to enable strong interactions with polarizable molecules such as CO2. Such pillared CPs offer relatively low cost, high stability and modularity. When these features are coupled with superior performance vs . other classes of porous materials in the context of carbon capture and other gas separations involving CO2, they are likely to gain increased attention in the future.

A 2‐D Grid Coordination Polymer with an In‐plane and Out‐of‐plane Structure Bridged by Pyrazine Spacers

AbstractA 2‐D grid copper(II) complex [Cu(μ3‐H2dpzpda)(N3)]n(ClO4)n (2) has been synthesized and structurally characterized. The copper atom in the complex is six‐coordinated in an octahedral geometry. The azide anions coordinated with copper in a 1‐end form, and the perchlorate anions are not coordinated to copper centers. The structure shows an orthogonal overlap of orbitals through the bridging pyrazine. Extensive hydrogen bonds were observed in 2D networks. Magnetic studies indicate the presence of very weak antiferromagneic coupling between copper(II) ions.

Donor disposition dependent dimensionality and in situ racemization in luminescent cadmium camphorate coordination polymers with dipyridylamide ligands

Hydrothermal reaction of cadmium nitrate, d-camphoric acid (H2d-cam), and either 3-pyridylnicotinamide (3-pna) or 3-pyridylisonicotinamide (3-pina) afforded coordination polymers whose dimensionality, topology, and chirality depend on the specific dipyridylamide isomer used. [Cd(d-cam)(3-pna)(H2O)2]n (1) displays a simple 1-D coordination polymer chain structure, anchored into a supramolecular 3-D lattice by inter-chain hydrogen bonding. In the case of the 3-pina dipyridylamide isomer, in situ racemization of d-cam occurred, producing [Cd(dl-cam)(3-pina)]n (2). Compound 2 has d-cam and l-cam ligands disordered over two sets of crystallographic positions. Compound 2 has 2-D (4,4) grid coordination polymer layer motifs in contrast to the 1-D structure of 1. Compounds 1 and 2 emit blue-violet light upon excitation with ultraviolet radiation, via π–π∗ molecular orbital transitions within the pyridyl rings of the dipyridylamide ligands. Thermal decomposition behavior is also discussed.

Synthesis and Characterization of Novel Copper(II) 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability

Two-dimensional (2D) grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf) with Cu(NO3)2 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf)2(NO3)2]·(biphenyl)2}n (1), {[Cu(bpf)2(NO3)2]·(m-C6H4(OMe)2)2}n (2), {[Cu(bpf)2(NO3)2]·PhtBu}n (3) and {[Cu(bpf)2(NO3)(H2O)]NO3·(bpf)0.5}n (4) were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3− anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds.

Synthesis and crystal structure of 2-D silver coordination polymers containing aminopyrazine

Two supramolecules of Ag(I), [Ag(NO3)(APZ)] n (1) and {[Ag(APZ)2][CF3COO] · H2O} n (2) (APZ = aminopyrazine) have been prepared by self-assembly of Ag(I) salts with APZ in MeOH/H2O. EA, IR, and TGA spectra have been recorded and the complexes have been structurally characterized by X-ray crystallography, confirming that 1 and 2 are 2-D pleated rectangular grid coordination polymers. The in 1 is coordinated to Ag+, bidentate, and μ2,η1-, while CF3COO− in 2 is not coordinated. Ag ··· O interactions, hydrogen bonds, and π ··· π stacking interactions support the supramolecular structures.

Two-dimensional rhombus grid coordination polymer showing heterogeneous catalytic activities

A coordination polymer, {[Cd(L) 2(DMF) 2]·(ClO 4) 2·(2DMF)} n ( 1) (L = bis-(4-imidazol-1-yl-phenyl)-diazene) has been synthesized at room temperature. The polymer forms a two-dimensional (2D) rhombus-grid sheet structure. These 2D sheets are stacked in ABAB… mode with an inter-planar spacing of 3.729 Å. Each Cd(II) ion is equatorially bonded to four imidazole N atoms belong to four different ligand units while O atoms from two DMF molecules occupy the axial sites. Two ClO 4 − counter anions as well as two DMF molecules occupy the void space in each rhombus grid. This compound catalyzes cyanosilylation reactions of aromatic aldehydes in dichloromethane under mild conditions in heterogeneous fashion. On heating 1 at 120 °C for 4 h, all DMF molecules are lost and the ClO 4 − anions move out of the void space to occupy the axial sites on the metal to yield, de-solvated {[Cd(L) 2(ClO 4) 2]} n ( 1) without losing crystallinity. De-solvated 1 exhibits heterogeneous catalytic activity in several Knoevenagel condensation reactions at RT.

A Square Grid Coordination Polymer from Tetrahedral Metal Ions and Angular Dicarboxylate Ligands

The title compound, {[NH2(CH3)2]4[Zn(C8H4O5)2](SO4)}n, is a coordination polymer based on mononuclear Zn(O2C)4 unit and 5-hydroxyisophthalate linker. The 120° arrangement of the two carboxyl groups of the ligand effectively cancels out the tetrahedral coordination angles around Zn2+ ion and results in a two-dimensional (2D) square grid network. The surplus cations and anions balancing the extra charges of the framework form hydrogen bonds with carboxyl and hydroxyl groups of adjacent 2D layers. As a result, straight open channels are formed along a direction perpendicular to the 2D layers. The combination of tetrahedral Zn2+ ions and angular dicarboxylate ligands leads to square-grid type layers that form straight open channels by interlayer stacking.

Syntheses, Structures, and Properties of Honeycomb and Square Grid Coordination Polymers with In Situ Formed 5-(2′-Pyrimidyl)tetrazolate

Solvothermal reactions of Zn(II), Cd(II), Mn(II), Co(II), or Ni(II) salts and 2-pyrimidinecarbonitrile (pymCN) in the presence of NaN3 in DMF yielded seven metal−organic coordination polymers formulated as [Zn(pymtz)2]n (1), [NaMII(pymtz)3]n·G (M = Zn 2, Cd 3, Mn 4, Co for 5, and Ni for 6; G = DMF and/or H2O) and [Cd(pymtz)2]n (7) [pymtz = 5-(2′-pyrimidyl)tetrazolato]. Compounds 2−6 are isomorphous and all contain neutral honeycomb layers in which pymtz serves as a bis(chelating) bridge between M(II) (M = Zn for 2, Cd for 3, Mn for 4, Co for 5, and Ni for 6) and Na+, and the ellipse stacking of the layers generates one-dimensional hexagonal channels. Compounds 1 and 7 exhibit different (4,4) square grid networks. In 1, the Zn ions are octahedrally coordinated and linked by pymtz ligands in the μ2 tridentate bridging mode, while in 7, the Cd(II) ions are eight-coordinated with a square prismatic geometry and bridged by bis(chelating) pymtz ligands. Compounds 2 and 3 can transform into 1 and 7, respectively...