1D Chain Coordination Polymer Research Articles

Synthesis, structure, and AP catalytic performance of two new 1D coordination polymers

Two 1D chain coordination polymers (CPs), [Co(DNDPA)(DMF)2] 1 and [Mn(DNDPA)(DMF)2] 2, were successfully synthesized (4,4′-dinitrodiphenic acid, DNDPA). Their structures were confirmed by single-crystal X-ray diffraction. Differential scanning calorimetry coupled with thermogravimetric analysis revealed that both CPs exhibit commendable thermal stability, with CP 1 and 2 decomposing at 368.9 °C and 375.5 °C, respectively. Non-isothermal kinetic studies confirmed that both CPs displayed significant catalytic activity for the decomposition of ammonium perchlorate (AP). In particular, CP 1 and 2 reduced the activation energy of AP from its intrinsic value to 100.5 kJ/mol and 127.45 kJ/mol, respectively, and its high-temperature decomposition peak to 354.3 °C and 327.7 °C, respectively. These findings underscore the potential of these CPs as effective catalysts for enhancing the combustion properties of AP.

Modulating Magnetic and Photoluminescence Properties in 2-Aminonicotinate-Based Bifunctional Coordination Polymers by Merging 3d Metal Ions.

Herein, the synthesis and study of bifunctional coordination polymers (CPs) with both magnetic and photoluminescence properties, derived from a heterometallic environment, are reported. As a starting point, three isostructural monometallic CPs with the formula [M(μ-2ani)2 ]n (MII =Mn (1Mn ), Co (3Co ) and Ni (4Ni ); 2ani=2-aminonicotinate), crystallise as chiral 2D-layered structures stacked by means of supramolecular interactions. These compounds show high thermal stability in the solid state (above 350 °C), despite which, in aqueous solution, compound 1Mn is shown to partially transform into a novel 1D chain CP with the formula [Mn(2ani)2 (μ-H2 O)2 ]n (2Mn ). A study of the direct current (dc) magnetic properties of 1Mn , 3Co and 4Ni reveals a spin-canted structure derived from antisymmetric antiferromagnetic weak exchanges along the chiral network (as confirmed by DFT calculations) and magnetic anisotropy of the ions, in such a way that long-range ordering is observed with variable magnitude for the spin carriers. Moreover, compounds 3Co and 4Ni show no frequency-dependent alternating current (ac) susceptibility curves under zero dc field; this is characteristic behaviour of a glassy state that may be partially supressed for 3Co by applying an external dc field. To overcome long-range magnetic ordering, CoII ions are diluted in a diamagnetic ZnII -based matrix, which enables single-molecule magnet behaviour. Interestingly, this strategy allows a bifunctional Cox Zn1-x 2ani material, which is imbued with a strong photoluminescent emitting capacity, as characterised by an intense blue light followed by a green afterglow, to be obtained.

Heterobimetallic [NiIILnIII] (Ln = Sm and Tb) N2O4-donor coordination polymers: Syntheses, crystal structures and fluorescence properties

Through the self-assembly of a 3-EtO salamo H2L with nickel acetate tetrahydrate, lanthanide nitrate hexahydrate (Ln = Sm and Tb) and terephthalic acid (H2bdc), two new heterobimetallic [NiIILnIII] 3d-4f polymers, 2∞[Ni(L)Sm(bdc)1.5]·CH3OH (1) and 1∞[Ni(L)Tb(NO3)(DMF)(bdc)] (2) were synthesized, respectively. Coordination polymers 1 and 2 were characterized via elemental analysis, X-ray single-crystal analysis, IR and UV–visible absorption spectroscopy. Coordination polymer 1 is a 2D coordination polymer in which [Ni(L)Sm] units are linked by exodentate (bdc)2− linker. Coordination polymer 2 is a 1D chain coordination polymer in which the [Ni(L)Tb(NO3)] moieties are connected by exodentate (bdc)2− linker, and they further form a 3D supramolecular configuration through intermolecular hydrogen bondings. Fluorescence properties of coordination polymers 1 and 2 have been discussed.

A luminescent sensor based on zinc(II) 1D chain coordination polymer for effective acetone detection

A novel Zn(II) coordination polymer, namely, [Zn(Hpzdc)(ncp)]n (1) was synthesized by the reaction of zinc(II), pyrazole-3,5-dicarboxylic acid (H3pzdc), and neocuproine (ncp) at ambient temperature. The single-crystal X-ray diffraction analysis revealed that each tetrahedral Zn(II) center is assembled by Hpzdc linker exhibiting 1D zigzag-like chain coordination polymer. The interchain hydrogen bonding and π-π stacking interactions stabilize a 3D supramolecular framework of 1. The photoluminescence in solid state and suspension of 1 exhibits blue emission at 418 nm. Moreover, the ethanolic suspension of 1 can be used to selectively detect acetone through the luminescent quenching (turn-off) process within 30 s. Compound 1 displays low detection limit (LOD) of 0.016 vol% without the interference of competitive solvents. Also, compound 1 can be reusable for three times.

Three new coordination polymers based on a fluorene derivative ligand for the highly luminescent sensitive detection of Fe3+

Three new 1D chain coordination polymers (CPs) [M(FDC) 2 (H 2 O) 2 ] n [M = Zn ( 1 ), Cd ( 2 )], [Cd(FDC) 2 (bpy)(H 2 O)] n ( 3 ) (HFDC = 9-fluorenone-4-carboxylic acid, bpy = 4,4′-bipyridine) were prepared by reactions of the corresponding metal salt with the fluorene derivative ligands of HFDC. Compounds 1 – 3 have been characterized by elemental analysis, IR, TGA, PXRD and single crystal X-ray diffraction. 1 and 2 are isomorphous. In 2 , Cd 2+ ions are joined by O atoms from coordinating water molecules and FDC − ligands, generating a 1D coordination polymer along the a axis, and 3 features a 1D chain structure in which adjacent Cd 2+ ions are linked by N atoms of bpy ligands. 1 – 3 are further extended to 3D supramolecular structures by O–H⋯O hydrogen bonds and π···π interactions. To the best of our knowledge, the title compounds are the first example of CPs based on the HFDC ligand. Moreover, 1 and 3 are good chemosensors for the detection of Fe 3+ with a low detection limit of 1.0 × 10 −6 M, indicating that 1 and 3 could be used as efficient fluorescent sensors with high sensitivity and selectivity for Fe 3+ . 1 and 2 are isomorphous. In 2 , Cd 2+ ions are joined by O atoms from coordinating water molecules and FDC − ligands, generating a 1D coordination polymer along the a axis, and 3 features a 1D chain structure in which adjacent Cd 2+ ions are linked by N atoms of bpy ligands. 1 and 3 are good chemosensors for the detection of Fe 3+ with a low detection limit of 1.0 × 10 −6 M, indicating that 1 and 3 could be used as efficient fluorescent sensors with high sensitivity and selectivity for Fe 3+ . • Three new one-dimensional coordination polymers based on the HFDC ligand have been purposefully synthesized. • 1 and 3 can be fluorescent probes with excellent sensitivity and selective detection for Fe 3+ in the water system. • The TGA reveals that compounds 1 and 2 possess good thermal stability.

Discrete versus Chain Assembly: Hexacyanometallate Linkers and Macrocyclic {3d-4f} Single-Molecule Magnet Building Blocks.

The self-assembly of macrocyclic tetranuclear 3d-4f single-molecule magnet (SMM) building blocks, [CuII3TbIII(LPr)(NO3)2(H2O)]NO3 (1), with K3[MIII(CN)6] linkers, where M = Fe, Cr, or Co, results in a range of discrete (monomer and dimer) and one-dimensional (1D) chain (coordination polymer) supramolecular architectures, which have been structurally and magnetically characterized. The outcome of reactions of 1 with an excess of K3[Fe(CN)6] has been probed in detail. It was found to be dependent on several factors, resulting in five distinctly different compounds, all of which have the same 1:1 ratio of [Cu3Tb(LPr)]3+ to [Fe(CN)6]3-, but which differ in structural type, solvent content, and magnetic behavior. Three are discrete complexes: monomeric {[Cu3Tb(LPr)(H2O)5][Fe(CN)6]·(H2O)3·(MeCN)]} (2) and [Cu3Tb(LPr)Fe(CN)6(H2O)4(MeCN)]·(H2O)2·(MeCN) (3) plus dimeric {[Cu3Tb(LPr)Fe(CN)6(H2O)4]·(H2O)6.75}2 (4), while two are 1D chains (coordination polymers): {[Cu3Tb(LPr) cis-Fe(CN)6(H2O)3(MeOH)]·(H2O)3.75·(MeOH)0.75} n (5) and {[Cu3Tb(LPr) trans-Fe(CN)6(H2O)4]·(H2O)5·(DMF)5]} n (6). When K3[Cr(CN)6] or K3[Co(CN)6] are used in place of K3[Fe(CN)6], a discrete dimer {[Cu3Tb(LPr)Cr(CN)6(H2O)4]·(H2O)2.75}2 (7) and a 1D chain coordination polymer {[Cu3Tb(LPr)Co(CN)6(H2O)3(MeOH)]·(H2O)4·(MeOH)} n (8) are obtained, respectively, which are isomorphous with 4 and 5, respectively. Magnetic studies reveal the paramagnetism of these compounds down to 1.8 K, except for 7, which displays an ordered antiferromagnetic ground state with metamagnetic behavior. The 1D-coordination polymers (5, 6, and 8) do not exhibit single-chain magnet properties, because of the very weak interbuilding block magnetic interactions. For chain 8, below 2.8 K, a clear nonzero out-of-phase signal is seen, similar to that seen for the building block 1, so the magnetism of 8 is governed by that of these SMM building blocks (1).

CuI-Based Coordination Polymer Assembled from a 2-Pyridyl Sulfide Ligand: Synthesis and Luminescent Properties

2-Ehtylthiopyridine (L) reacts with CuI (MeCN, r.t.) to afford a 1D chain coordination polymer (CP), [Cu2I2(L)]n in a 75% yield. The latter consists of double-stranded (Cu2I2)n ribbons ligated on both sides by 2-ehtylthiopyridines in a 1,3-N,S bridging manner. In the solid state at 298 K, this CP displays yellow-green photoluminescence (λmax = 550 nm) with a short lifetime (2.4 µs) and a moderate emission quantum yield (16%).

A series of new pyridine carboxamide complexes and self-assemblies with Tb(III), Eu(III), Zn(II), Cu(II) ions and their luminescent and magnetic properties

In this study, we present eight new complexes and self-assemblies of Tb(III), Eu(III), Zn(II) and Cu(II) ions with novel pyridine carboxamides, L1 [methyl 4-methyl-3-(pyridine-4-carbonylamino)benzoate] and L2 [methyl 2-methyl-3-(pyridine-4-carbonylamino)benzoate], as heterocyclic ligands. Two luminescent and spatially organized coordination compounds were obtained with the use of the solvothermal synthesis method, (1) [Tb3(L1)4(BTC)3(H2O)3] (where BTC is benzene-1,3,5-tricarboxylic acid) and (5) [Eu(L2a)3(H2O)3](H2O)4. As a result of one pot reaction synthesis under reflux the d-electron metal ions and self-organization of ligands gave complexes (2) [Zn(L1)2Cl2], (3) [Cu(L1)2(SCN)2(H2O)], (4) [Cu(L1)2Cl2], hybrid salt (6) [(CuCl4)2-(L2b)22+](H2O), (7) [Cu(L2)2Cl2] and 1D-chain coordination polymer (8) [Cu(L2)2(SCN)2]. Identification of the obtained compounds was performed on the basis of the excitation, emission, 1H NMR, FT-IR spectra, luminescence lifetimes, SEM images, PXRD, single-crystal X-ray diffraction, MS, TGA and elemental analysis. Selected compounds were also analyzed in terms of their potential magnetic properties.

CuI-based coordination polymer assembled from a 2-pyridyl sulfide ligand: Synthesis and luminescent properties

2-Ehtylthiopyridine (L) reacts with CuI (MeCN, r.t.) to afford a 1D chain coordination polymer (CP), [Cu2I2(L)]n in a 75 % yield. The latter consists of double-stranded (Cu2I2)n ribbons ligated on both sides by 2-ehtylthiopyridines in a 1,3-N,S bridging manner. In the solid state at 298 K, this CP displays yellow-green photoluminescence (λmax = 550 nm) with a short lifetime (2.4 μs) and a moderate emission quantum yield (16 %).

Diverse interpenetration schemes and topologies in cobalt coordination polymers constructed from 2-carboxycinnamic acid and a long-spanning dipyridylpiperazine ligand

Hydrothermal reaction of cobalt nitrate, 2-carboxycinnamic acid (H2cca), and a long-spanning dipyridyl-type ligand resulted in three coordination polymers that were characterized by single crystal X-ray diffraction and manifested different structural topologies and interpenetration schemes. {[Co(cca)(4-bpmp)(H2O)2]·4H2O}n (1, 4-bpmp = bis(4-pyridylmethyl)piperazine) shows a 2-fold interpenetrated 4-connected 66dia network. Use of the dipyridylamide bis(4-pyridylformyl)piperazine (4-bpfp) produced a crystalline mixture of the major product 3D 6-connected 41263pcu network coordination polymer {[Co(cca)(4-bpfp)]·2H2O}n (2) and the minor product 1D chain coordination polymer [Co(dibf)2(4-bpfp)(H2O)2]n (3, dibf = 3-dihydro-3-oxo-1-isobenzofuranacetate). The in situ rearrangement of 2-carboxycinnamic acid in the presence of 4-bpfp produced the anionic lactone dibf in 3. Thermal decomposition behavior of the new major product phases was probed.

Versatility of copper(II) coordination compounds with 2,3-bis(2-pyridyl)pyrazine mediated by temperature, solvents and anions choice

Tuning reaction temperatures as well as the variation in starting copper salts and solvents led to the formation of a new series of Cu(II) coordination compounds with 2,3-bis(2-pyridyl)pyrazine (dpp): a mononuclear [Cu(acac)(dpp)(NO3)] (1) complex, two dinuclear [Cu2(acac)2(dpp)(NO3)(H2O)]NO3 (2) and [Cu2(Hdpp)2(ox)(Cl)2(H2O)2]Cl2·6(H2O) (4) complexes, and four coordination polymers {[Cu4(dpp)2(ox)(Cl)6]}n (3), {[Cu4(dpp)2(ox)(NO3)6(H2O)2]∙1.2(H2O)}n (5), {[Cu(dpp)(NO3)](NO3)·(H2O)}n (6) and {[Cu(dpp)(SO4)(H2O)2]}n (7), where acac− = acetylacetonate, ox2− = oxalate. Remarkably, the treatment of Cu(II) chloride dihydrate with dpp in methanol solution led to an unusual in situ condensation of dpp with acac− to produce [Cu2(acdpp)2(Cl)4]·2(MeOH) (8). The structure of 1 consists of neutral, mononuclear [Cu(acac)(dpp)(NO3)] units with acac− and dpp acting as bidentate ligands. In 2, the dpp ligand coordinates in a bis-chelating mode to two Cu(II) ions and bridges them into a dimeric entity, whereas an oxalate linker joins [Cu(Hdpp)(Cl)2(H2O)]+ units into a dimer in 4. Compounds 3, 5, 6 and 7 are 1D chain coordination polymers, which incorporate two symmetry independent metal centers and different bridging ligands: Hdpp+ as a protonated cationic or dpp as a neutral chelating ligand and oxalate, Cl− anions or sulfate di-anions as bridging ligands. Magnetic studies were performed on samples 1 and 2, and the analysis reveals a very weak magnetic exchange coupling mediated via the dpp ligand.

Copper(II) coordination polymers containing neutral trinuclear or anionic dinuclear building units based on pyrazole-3,5-dicarboxylate: Synthesis, structures and magnetic properties

Four novel copper(II) coordination polymers, namely {[Cu3(pzdc)2(pyz)(H2O)6](H2O)}n (1), {[Cu3(pzdc)2(bpy)(H2O)8](H2O)6}n (2), {[Cu4(Hpzdc)2(pzdc)2(bpy)2][Cu(bpy)(H2O)4]n(H2O)4}n (3), and {[Cu3(pzdc)2(ampy)(H2O)5](H2O)3}n (4) (H3pzdc=pyrazole-3,5-dicarboxylic acid, pyz=pyrazine, bpy=4,4′-bipyridine and ampy=2-aminopyrazine) were synthesized and characterized. Compounds 1, 2 and 4 were synthesized by layering method at room temperature while 3 was prepared under solvothermal reaction. Compounds 1 and 2 are one-dimensional (1D) chain coordination polymers, while 3 shows 1D cationic chain coordination polymer with anionic tetranuclear Cu(II) cluster. Compound 4 exhibits 1D ladder-like chain structure. Compounds 1, 2 and 4 consist of neutral trinuclear [Cu3(pzdc)2] building unit which is constructed by μ2-pzdc3− bridging (5-6-5), (6-6-6), and (6-5-5) sequences of Cu(II) geometries for 1, 2 and 4, respectively. Each trinuclear unit is extended via N,N′-linkers giving polymeric chain structure. In contrast, anionic tetranuclear cluster of 3 is built up from two anionic dinuclear metallacyclic [Cu2(Hpzdc)(pzdc)]− building units and double μ2-bpy spacers. The magnetic properties of 1, 2 and 4 exhibit weak antiferromagnetic interactions among Cu(II) centers.

Synthesis, structure, luminescence and photocatalytic properties of an uranyl-2,5-pyridinedicarboxylate coordination polymer

An uranium coordination polymer, namely [(UO2(pydc)(H2O)]·H2O (1) (H2pydc=2,5-pyridinedicarboxylic acid), has been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 1D chain coordination polymer, in which UO22+ ions are bridged by 2,5-pyridinedicarboxylate ligands and the chains are connected into a 3D supramolecular network by O–H···O hydrogen bond interactions and π–π stacking interactions. The photocatalytic properties of 1 for degradation of methylene blue (MB), Rhodamine B (RhB) and methyl orange (MO) under Hg-lamp irradiation have been performed, and the amount of the catalyst as well as Hg-lamp irradiation with different power on the photodegradation efficiency of MB have been investigated. Elemental analyses, infrared spectroscopy, TG-DTA analyses and luminescence properties were also discussed.

Structural diversity and luminescent properties of cyanoacetato zinc/cadmium coordination polymers with N,N′-ditopic auxiliary ligands

By using the carboxylate ligand cyanoacetate (cna) and N,N′-ditopic organic neutral spacers, four new Zn(II)/Cd(II) coordination polymers, formulated as [Zn(cna)2(bpy)(H2O)2]n (1), [Cd3(cna)6(bpy)3]n (2), [Zn(cna)2(bpa)]n (3) and [Cd(cna)2(bpa)]n (4) (bpy=4,4′-bipyridyl and bpa=1,2-di(4-pyridyl)ethane) have been obtained. All compounds exhibit one-dimensional (1D) chain coordination polymers with diverse topologies. Compound 1 reveals a linear chain structure which is formed by μ2-bpy bridging between [Zn(cna)2(H2O)2]n units. Compound 2 shows a triple-stranded chain consisting of six- and seven-coordinated Cd(II) centers. Compound 3 exhibits a zigzag chain coordination polymer containing μ2-bpa spacers bridging between tetrahedral Zn(II) ions. Whereas 4 shows a ladder-like structure which is built from double μ2-bpa spacers connecting between Cd(II) cyanoacetate dimeric units. All compounds are further extended into a 3D supramolecular architectures through non-covalent weak hydrogen bonds and N⋯π and/or C–H⋯π interactions. The free bpa ligand exhibits very weak photoluminescence in the solid state, while this property is significantly enhanced in 3 and 4.

Structural diversity of four 1D chain coordination polymers based on chiral N-tosyl-L-glutamic acid: Effect of metal ions and N-donor ancillary ligands

Four one-dimensional (1D) coordination polymers {[Cd2(tsgluO)2(3-ampy)5]·2.5H2O}n (1), {[Zn(tsgluO)(3-ampy)(H2O)]·2H2O}n (2), [Cd(tsgluO)(Him)(H2O)]n (3), and [Cd(tsgluO)(1,10-phen)]n (4) (H2tsgluO=N-tosyl-L-glutamic acid, Him=imidazole, 3-ampy=3-amino pyridine, phen=1,10-phenanthroline) were synthesized and characterized using elemental analysis, infrared spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. Compound 1 crystallizes in space group C2/c, and features a 1D double helix structure. Compound 2 crystallizes in chiral space group P21, exhibits a 1D linear single-chain structure that is extended by hydrogen-bonding interactions to form a 2D supramolecular network. Compounds 3 and 4 crystallize in chiral space groups P21 and P212121, respectively; these compounds exhibit 1D ladder-like double-chain structures, and the chains of 3 are extended by hydrogen-bonding interactions to form a 2D supramolecular network. The structural diversity of these compounds is attributed to the effect of metal cations and N-donor ancillary ligand. Furthermore, the solid-state fluorescence properties of compounds 1–4 were studied at room temperature. The circular dichroism (CD) of compounds 2 and 3 was also investigated.

Syntheses, crystal structures and antioxidant study of Zn(II) complexes with morin-5′-sulfonic acid (MSA)

The study of modified synthetic procedure of water soluble morin-5′-sulfonic acid sodium salt (NaMSA) involving less aggressive chemicals and carried out at mild conditions was described. The NaMSA salt is a convenient source of anionic morin-5'-sulfonic ligand (MSA) in ion exchange reactions. The coordination ability of MSA ligand towards the zinc cations was investigated in aqueous solution and in solid state. Novel zinc complexes of morin-5'-sulfonate were obtained by a reaction of Zn(NO3)2 with morin-5'-sulfonate in water. Resulting compounds were characterized by single-crystal X-ray diffraction analysis, as well as spectral and thermal methods. The coordination interaction, hydrogen bond and π–π stacking lead to the formation of a 1D chain or 3D coordination polymers. The antioxidant activity of the Zn(II)–MSA complexes was evaluated by means of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method. In this work, we have shown that the studied compounds are more effective free radical scavengers than the natural flavonoids like plain morin.

Synthesis, Crystal Structure, and Thermal Stability Properties of a Novel 1D [Co (II) Coordination Polymer Co(L)(4,4′-Bipy)(H2O)

A 1D chain coordination polymer, namely, [Co(L)(4,4′-Bipy)(H2O)]n (1), where Na2L = 2-[(2-Hydroxy-benzylidene)-amino]-benzenesulfonic acid sodium salt and 4,4′-Bipy = 4,4'-bipyridine, has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P2(1)/n. The sulfonate-derived Schiff base serves as a common N, O, O′-tridentate ligand and 4,4′-Bipy in the complex (1) act as μ2-bridging ligand linking adjacent two metal ions into 1D zigzag infinite chain. The 1D chain is further constructed into 3D networks via intermolecular hydrogen bonds between the phenolato oxygen atom and coordinated water.

Dipyridylamide Donor Disposition and Isophthalate Substituent Steric Effect on the Dimensionality and Topology of Divalent Copper Coordination Polymers

AbstractDivalent copper coordination polymers containing an isophthalate ligand and a dipyridylamide ligand show different dimensionalities and topologies depending on pyridyl nitrogen donor disposition and the steric bulk of the substituent on the dicarboxylate aromatic ring. According to single‐crystal X‐ray diffraction, [Cu(ip)(3‐pna)]n (1, ip = isophthalate, 3‐pna = 3‐pyridylnicotinamide) shows a (4, 4) layered grid structure based on {Cu2(OCO)2} dimeric units. {[Cu(ip)(3‐pina)]·H2O}n (2, 3‐pina = 3‐pyridylisonicotinamide) exhibits similar dimeric units, but in contrast to 1 these are connected into a non‐interpenetrated 3D 658 cds network. Both [Cu(mip)(3‐pina)]n (3, mip = 5‐methylisophthalate) and [Cu(meoip)(3‐pina)]n (4, mip = 5‐methoxyisophthalate) display dimer‐based 41263 pcu networks in contrast to 2. Use of 5‐hydroxyisophthalate (H2hip) as a precursor afforded a mixture of {[Cu2(hip)2(3‐pina)4]·9.5H2O}n (5) and [Cu(hip)(3‐pina)]n (6). Compound 5 shows a 2D interdigitated structure with [Cu(hip)]n coordination polymer layers featuring {Cu2(OCO)2} dimeric units and pendant 3‐pina ligands, while 6 also showed a dimer‐based 41263 pcu network. Use of the very sterically bulky 5‐tert‐butylisophthalate (tbip) ligand afforded the 1D chain coordination polymer {[Cu(tbip)(3‐pina)2(H2O)]·H2O}n (7), which contains isolated copper ions in contrast to 1–6, and has a curious “butterfly“ resemblance. Very weak antiferromagnetic coupling is seen within the {Cu2(OCO)2} dimeric units in 1. Thermal decomposition behavior is also discussed.

Influence of the counter ion on the structure of two new copper(I) coordination polymers: Synthesis, structural characterization and thermal analysis

Two new coordination polymers [Cu2(μ3-SCN)2(μ-bbd)]n (1) and {[Cu(μ-bbd)1.5](PF6)}n (2) were synthesized by the reactions of 1,4-bis(3,5-dimethylpyrazol-1-yl)butane (bbd) with the corresponding copper(I) salts, in order to evaluate the effect of the counter anion on the structure of the resulting products. The structure of these compounds were determined by X-ray crystallography; Compound 1 is a 2D coordination polymer, in which the thiocyanate ligand adopts uncommon μ3-1κ1N;2:3κ2S coordination mode to link three tetrahedrally coordinated copper centers. The fourth coordination site on each copper atom is occupied by a pyrazole nitrogen atom belonging to a μ-bbd ligand. In contrast to 1, 2 is a 1D chain coordination polymer in which the copper atoms, adopting a distorted trigonal planar geometry, are linked by bridging bbd ligands having alternately two different conformations. The results indicate that the use of a coordinating counter anion as thiocyanate which is capable of bridging more than one metal center instead of non-coordinating hexafluorophosphate anion, promotes the formation of a 2D polymer over a 1D polymeric chain. The complexes have also been characterized by elemental analysis, IR spectroscopy, XRPD and thermal analysis.

Study on 1D Chain Coordination Polymer of Cinnamaldehyde Salicyl Hydrazone Cadmium Complex

A one-dimensional (1D) chain coordination polymer [Cd2L4(DMF)2]n (HL = C16H14N2O2) has been synthesized and characterized by physicochemical and spectroscopic methods, cyclic voltammetry and single crystal X-ray structure analysis. The complex crystallizes in the monoclinic system, and each Cd(II) of the complex is a six-coordinate with a distorted octahedral geometry. Cinnamaldehyde salicylhydrazone, C16H14N2O2 as bridging ligands, links the neighboring Cd(II) atoms in a head-to-tail mode. They construct an infinite zigzag chain along the c axis. Cyclic voltammetry shows that the complex has a weak reductive centered at −0.328 V and an oxidative peak at 0.410 V. Fluorescence spectra indicate that the band of complex at 285 nm has a 30 nm red-shift compared with HL.