Bridged Coordination Polymers Research Articles

Hofmann-Type Cyanide Bridged Coordination Polymers for Advanced Functional Nanomaterials.

Since the discovery of Hofmann clathrates of inorganic cyanide bridged coordination polymers (Hofmann-type CN-CPs), extensive research is done to understand their behavior during spin transitions caused by guest molecules or external stimuli. Lately, research on their nanoscale architectures for sensors and switching devices is of interest. Their potential is reported for producing advanced functional inorganic materials in two-dimensional (2D) morphology using a scalable solid-state thermal treatment method. For instance, but not restricted to, alloys, carbides, chalcogenides, oxides, etc. Simultaneously, their in situ crystallization at graphene oxide (GO) nanosheet surfaces, followed by a subsequent self-assembly to build layered lamellar structures, is reported providing hybrid materials with a variety of uses. Hence, an overview of the most recent developments is presented here in the synthesis of nanoscale structures, including thin films and powders, using Hofmann-type CN-CPs. Also thoroughly demonstrated are the most recent synthetic ideas with the modest control over the size and shape of nanoscale particles. Additionally, in order to create new functional hybrid materials for electrical and energy applications, their thermal decomposition in various environments and hybridization with GO and other guest molecules is examined. This review article also conveyed their spin transition, astounding innovative versatile adhesives, and structure features.

Sequential Water Sorption/Desorption of a Nonporous Adaptive Organic Ligand Bridged Coordination Polymer for Atmospheric Moisture Harvesting.

Moisture harvesters with favourable attributes such as easy synthetic availability and good processability as alternatives for atmospheric moisture harvesting (AWH) are desirable. This study reports a novel nonporous anionic coordination polymer (CP) of uranyl squarate with methyl viologen (MV2+ ) as charge balancing ions (named U-Squ-CP) which displays intriguing sequential water sorption/desorption behavior as the relative humidity (RH) changes gradually. The evaluation of AWH performance of U-Squ-CP shows that it can absorb water vapor under air atmosphere at a low RH of 20 % typical of the levels found in most dry regions of the world, and have good cycling durability, thus demonstrating the capability as a potential moisture harvester for AWH. To the authors' knowledge, this is the first report on non-porous organic ligand bridged CP materials for AWH. Moreover, a stepwise water-filling mechanism for the water sorption/desorption process is deciphered by comprehensive characterizations combining single-crystal diffraction, which provides a reasonable explanation for the special moisture harvesting behaviour of this non-porous crystalline material.

A novel mixed azido/phenoxido bridged 1D CuII coordination polymer containing o-vanillin-based compartmental ligand: Synthesis, magnetism, phenoxazinone synthase and catalytic activity in epoxidation of alkenes

A novel 1-D coordination polymer, formulated as [Cu2(L)(N3)3]·H2O (1), has been synthesized by reacting the Schiff base ligand, 2-methoxy-6-((2-(2-hydroxyethylamino)ethylimino) methyl)-phenol (HL), with copper(II) chloride dihydrate in the presence of sodium azide. The X-ray structural analysis shows that compound 1 consists of tetranuclear [Cu2(L)(N3)3]2 units bearing a central double asymmetric μ1,1-N3 bridge and terminal mixed µ1,1-N3/phenoxido bridges that are linked via a double µ1,1,3-N3 bridge forming a 1-D network. The magnetic properties of 1 show the presence of ferromagnetic Cu···Cu interactions through the central double μ1,1-N3 bridge (J1 = 81.7(3) cm−1) coexisting with antiferromagnetic Cu···Cu interactions through the double µ1,1-N3/phenoxido bridge (J2 = –62.3(4)cm−1). Additionally, there is a very weak antiferromagnetic interaction (zJ = –0.12(2) cm−1) through the asymmetric µ1,1,3-N3 bridge connecting the tetranuclear units. Using o-aminophenol (OAP) as a substrate, the phenoxazinone synthase-like catalytic activity of the CuII coordination polymer 1 has been studied. The compound efficiently catalyzes the aerobic oxidation of o-aminophenol in DMF medium with a turnover number Kcat = 31.69 h−1. Moreover, 1 has been used as an active catalyst for the epoxidation of cis-cyclooctene, as a model alkene, with tert-butyl hydroperoxide (TBHP), showing an excellent epoxide yield and selectivity in CHCl3 under reflux conditions. To enlarge the scope of the reaction, the efficacy of the catalytic method has also been investigated in the epoxidation of some other substituted alkenes.

Synergistic nanostructuring of CoNi-carbide/reduced graphene oxide derived from porous coordination polymers for high-performance hybrid supercapacitors

Porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have emerged as promising materials for nanostructuring inorganic functional materials with applications in energy storage. In this study, our aim was to synthesize CoNi-carbide (CoNi-C)/reduced graphene oxide (rGO) hybrids by annealing CoNi-cyanide bridged coordination polymers (CoNi-CP) under a nitrogen atmosphere. The resulting CoNi-C/rGO hybrids exhibited exceptional electrochemical performance, surpassing the individual components (CoNi-C and rGO). The hybrids demonstrated a specific capacitance of 1177 F g−1 and an electroactive surface area of 130.87 m2 g−1. By optimizing the CoNi-C/rGO ratio, we achieved the highest specific capacitance. Furthermore, we constructed a coin cell using CoNi-C/rGO-2 as the positive electrode and rGO as the negative electrode, which showed excellent performance with an energy density of 31.6 Wh kg−1 at a power density of 750 W kg−1 and capacitive retention of 84 % over 8000 charging cycles. Our findings provide valuable insights into designing and developing high-performance electrode materials for energy storage, with potential applications in various devices.

Oxalato bridged coordination polymer of manganese(iii) involving unconventional O⋯π-hole(nitrile) and antiparallel nitrile⋯nitrile contacts: antiproliferative evaluation and theoretical studies

Unconventional O⋯π-hole(nitrile) and antiparallel nitrile⋯nitrile contacts have been theoretically investigated for a Mn(iii) coordination polymer considering cytotoxicity, apoptosis, ROS generation, molecular docking and pharmacophore features.

Synthesis, crystal structure and dielectric properties of a new acetate bridged coordination polymer: {[La(μ-CH3COO)(PDC)(H2O)2].2H2O}n

An acetate bridged coordination polymer of lanthanum, formulated as {[La(μ-CH3COO)(PDC)(H2O)2].2H2O}n (H2PDC = pyridine-3,4-dicarboxylic acid) has been successfully grown by single gel diffusion technique at room temperature using hydrosilica gel and further characterized by elemental analysis, powder X-ray diffraction, FT-IR and UV–visible spectral studies. The compound crystallizes in triclinic space group, Pī. The metal centre is nine coordinated by oxygen atoms to form distorted tri-capped trigonal prism geometry. Single crystal X-ray diffraction studies reveal that the compound exists as one dimensional polymeric chain which is further assembled into 2D supramolecular framework via extensive hydrogen bonding. The dielectric and thermal decomposition behaviour of the sample was also studied.

Bimetallic Complexes of Group 8, 9, and 11 Metals Bridged by RB(NCH2PPh2)2C6H4 (R = H, 4‐C6H4X; X = H, Me, F) Ligands

The 1‐aryl‐2,1,3‐diazaboroles ArB(NCH2PPh2)2C6H4 (Ar = C6H5 1a, 4‐MeC6H4 1b, 4‐FC6H4 1c) result from the reactions of ArBCl2 with 1,2‐(NHCH2PPh2)2C6H4 in the presence of triethylamine. The reactions of these new proligands in addition to the parent diazaborole HB(NCH2PPh2)2C6H4 (4) with a range of metal precursors [Ru2(µ‐Cl)2Cl2(η6‐1,3,5‐Me3C6H3)2], [M2(µ‐Cl)2Cl2(η5‐C5Me5)2], [M2(µ‐Cl)2(η4‐C8H12)2] (M = Rh, Ir) and [AuCl(SC4H8)] have been explored. Rather than forming chelating, bidentate mono‐metallic complexes, these ligands are found to support the formation of bimetallic complexes without any indication of B–C activation (oxidative addition, transmetallation etc.). In the presence of excess 1a–b, iridium is found to form ligand bridged coordination polymers.

A nanoporous palladium(II) bridged coordination polymer acting as a peroxidase mimic in a method for visual detection of glucose in tear and saliva.

A nanoporous coordination polymer (NPCP) was prepared from palladium(II) chloride and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole and is shown to act as a peroxidase mimetic. It can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 which is formed on enzymatic oxidation of glucose by glucose oxidase. Based on these findings, a sensitive glucose test was worked out at 652nm where the intensity if the greenish-blue product is related to the actual concentration of glucose. Figures of merit include (a) rather low Km value (30μM) which evidences the strong binding affinity of the NPCP toward glucose, (b) a high v(max) (8.5M·s-1), (c) a 47nM detection limit, (d) a lifetime of a month, (e) a wide working pH range (2-10), and (f) a 25-80°C temperature range. The assay was applied to non-invasive determination of glucose assay in tear, saliva where the detection limits are found to be 61 and 91nM, respectively. Graphical abstract DSchematic of the mechanism of the peroxidase like catalytic activity of AHMT-Pd NPCPthat was applied in a selective colorimetric method for glucose detection based on TMB oxidation inthe presence of enzymatically generatedH2O2.

Arylazoimidazole Coordinated and Naphthalene-Dicarboxylato Bridged Polymers of Co(II) and Photochromic Zn(II) Complexes

Naphtheledicarboxylato ((NDC2–) bridged coordination polymers (CPs) along with (E)-1-methyl-2-(p-chlorophenylazo)imidazole (ClPai-Me) coordination to Co(II), [Co(∝-NDC)0.5(∝4-NDC)0.5(ClPai-Me)]·0.5H2O (1), and to Zn(II), [Zn(∝-NDC)0.5(∝4-NDC)0.5(ClPai-Me)]·0.5H2O (2), have been characterized. In the single crystal X-ray structure of 1, ClPai-Me chelates to the Co(II) ion by N(azo) and N(imidazolyl), whereas in compound 2, it acts as a monodentate N(imidazolyl) donor to the Zn(II) ion. The coordination atmosphere around Co(II) in the 1 ion is distorted octahedral CoN2O4, whereas in the case of 2, it is distorted square pyramidal ZnNO4. Compounds 1 and 2 exhibit the right-handed (P) and left-handed (M) one-dimensional helical chain. NDC–2 is serving as a bridge between two M(II) ions to constitute μ-NDC and four M(II) ions to construct μ4-NDC to assemble three-dimensional polymers. Upon UV light (369 nm) irradiation, compound 2 shows trans-to-cis isomerization of -N═N–C6H4–Cl-p both in the solid and solutio...

Synthesis, Crystal Structure and Magnetic Properties of [Mn((1R, 2R)‐Salcy)N3/NCS] Complexes: Solvent Dependent Crystallization of Monomers, Chains and Dimers.

AbstractFive new chiral MnIII complexes [Mn((1R, 2R)‐Salcy)N3]∞⋅CH3CN (1), [Mn((R,R)‐Salcy)N3]∞ (2), [Mn((R,R)‐Salcy)N3] (4), [Mn((R,R)‐Salcy)(H2O)N3]⋅C4H8O (5) and [Mn((R,R)‐Salcy)NCS] (6) have been synthesized and characterized by X‐ray structural analysis and magnetic measurements (Salcy=N,N′‐bis(salicylidene)‐1,2‐diaminocyclohexane}. The four azido complexes have been obtained from the previously known [Mn((R,R)‐Salcy)(CH3OH)N3] (3) by crystallization from various solvents. Compounds 1 and 2 are trans‐μ‐1,3‐azide bridged coordination polymers. While 1 forms helical chains, the chain in 2 is formed via translation of a dimeric helicate repeat unit. Compound 3 is a methanol coordinated mononuclear azido complex which forms a 2D‐network through H‐bonding. Compounds 4 and 6 are phenoxo‐bridged dimers without inversion center. Compound 5 is an aqua coordinated mononuclear azido complex, which forms a 1D‐chain through O−H⋅⋅⋅N hydrogen bonding involving axial ligands. In all six compounds MnIII exhibits a characteristic Jahn−Teller elongation. The magnetic coupling in 1 and 2 leads to antiferromagnetic interaction along the chain (2 J=−11.6 cm−1 for 1 and –11.9 cm−1 for 2) through the μ‐1,3‐azide bridge. Compound 3 is weakly antiferromagnetic due to hydrogen bonding interactions in the lattice. The phenoxo dimers (4 and 6) do not have measurable exchange interaction, the low temperature susceptibility being influenced mainly by zero‐field splitting.

Cyanide bridged coordination polymer nanoflakes thermally derived Ni3C and fcc-Ni nanoparticles for electrocatalysts

We have reported a controlled crystal growth process, which allows the formation of NiCNNi CP nanoflakes derived Ni3C and fcc-Ni nanoparticles.

Ultrafine Alloy Nanoparticles Converted from 2D Intercalated Coordination Polymers for Catalytic Application

Supported multimetallic alloy nanoparticles (NPs) have shown great potential for applications owing to combined functions of constituent metals, and more remarkably, enhanced physicochemical properties and even novel synergistic effects that are not possessed by their parent metals. Nevertheless, synthesizing this kind of nanocomposites has been a long‐standing challenge using conventional wet chemistry. Here, this study reports an efficient, versatile strategy for the preparation of multimetallic alloy NPs supported by layered double hydroxides (LDH) and/or layered double oxides (LDO). In this approach, different metal precursors are intercalated stepwise into the gallery space of LDH. Along with the coordination reaction between the metal precursors, 2D cyanide bridged coordination polymers (CP) are formed in the confined space. Afterward, supported multimetallic alloy NPs can be obtained via either liquid‐phase reduction or thermal autoreduction. Due to the homogeneous mixing of metals in the 2D CP, ultrafine alloy NPs can be obtained with high particulate uniformity and compositional tailorability. A large series of supported binary alloy NPs (FePd, FePt, CoPd, CoPt, NiPd, NiPt, and PtPd) and ternary alloy NPs (FePdPt, FeNiPt, FeCoPt, and NiCoPt) are successfully synthesized with this approach. The resulting supported multimetallic alloy NPs present great potential in numerous applications. To demonstrate their workability, one class of LDH/NiPd nanocomposite is explored as a model heterogeneous catalyst with respect to the carbon–carbon cross‐coupling reactions (Suzuki–Miyaura, Heck, and Sonogashira cross‐coupling reactions).

Self-Construction from 2D to 3D: One-Pot Layer-by-Layer Assembly of Graphene Oxide Sheets Held Together by Coordination Polymers.

Deposition of Ni-based cyanide bridged coordination polymer (NiCNNi) flakes onto the surfaces of graphene oxide (GO) sheets, which allows precise control of the resulting lamellar nanoarchitecture by in situ crystallization, is reported. GO sheets are utilized as nucleation sites that promote the optimized crystal growth of NiCNNi flakes. The NiCNNi-coated GO sheets then self-assemble and are stabilized as ordered lamellar nanomaterials. Regulated thermal treatment under nitrogen results in a Ni3 C-GO composite with a similar morphology to the starting material, and the Ni3 C-GO composite exhibits outstanding electrocatalytic activity and excellent durability for the oxygen reduction reaction.

Self‐Construction from 2D to 3D: One‐Pot Layer‐by‐Layer Assembly of Graphene Oxide Sheets Held Together by Coordination Polymers

AbstractDeposition of Ni‐based cyanide bridged coordination polymer (NiCNNi) flakes onto the surfaces of graphene oxide (GO) sheets, which allows precise control of the resulting lamellar nanoarchitecture by in situ crystallization, is reported. GO sheets are utilized as nucleation sites that promote the optimized crystal growth of NiCNNi flakes. The NiCNNi‐coated GO sheets then self‐assemble and are stabilized as ordered lamellar nanomaterials. Regulated thermal treatment under nitrogen results in a Ni3C–GO composite with a similar morphology to the starting material, and the Ni3C–GO composite exhibits outstanding electrocatalytic activity and excellent durability for the oxygen reduction reaction.

Synthesis, crystal structure and Thermogravimetry of ortho-phthalic acid bridged coordination polymer of Copper(II)

Coordination polymer of Cu(II) bridged by o-phthalic acid alone is not known. The reaction of CuCl2.2H2O with (2-butoxycarbonyl)benzoic acid yielded three dimensional coordination polymer bridged by o-phthalic acid. X-ray crystal structure shows structure with monoclinic P21/c space group. o-Phthalic acid molecules act as bridge between two Cu(II), one carboxylate binds to one Cu(II) as bidentate while the other carboxylate binds to another Cu(II) as monodentate. The four planar co-ordination positions of Cu(II) are satisfied by two chelated carboxylates while fifth and sixth co-ordination positions are satisfied by monodentate carboxylates. EPR and TGA of the coordination polymer are also reported. The reaction of CuCl2.2H2O with (2-butoxycarbonyl)benzoic acid yielded three dimentional coordination polymer where o-phthalic acid acts as bridge between Cu(II) centres. The X-ray crystal structure shows monoclinic P21/c space group with one carboxylate of o-phthalic acid binds to one Cu(II) as bidentate while the other carboxylate binds to another Cu(II) as monodentate.

Structural and Magnetic Studies of Novel 1-D Cyanido-bridged [CuII(Me2en)][CuII(Me2en)2][MoIV(CN)8]6H2O Chain

Background: The design, synthesis and physicochemical characterization of new switchable magnetic materials is among the most important tasks in the search of multifunctional compounds. Along these lines, intense efforts are focused on the investigation of cyanido–bridged coordination polymers: Prussian Blue Analogs and bimetallic coordination networks constructed of octacyanidometallates. Within this family, the CuII–[Mo(CN)8]4- assemblies have been extensively studied for their photomagnetic properties. The main aim of this work was the design, synthesis, as well as structural, spectroscopic and magnetic characterization of novel molecular material based on copper(II) complex with aliphatic bidentate polyamine and octacyanidometallate( IV) which shows a high number of cyanido bridges. The consequent objective was the study of potential photomagnetic properties of this new material. Methods: A newly synthesized compound [CuII(Me2en)][CuII(Me2en)2][MoIV(CN)8]·6H2O (1), Me2en = N,N– dimethylethylenediamine, was investigated structurally using single crystal X-ray diffraction, spectroscopically by studying IR and UV/Vis spectra, and photo- and magnetically characterized by studying its magnetic response in the dark and under irradiation in a variety of magnetic fields and temperatures. Results: Incorporation of N,N–dimethylethylenediamine (Me2en) into the CuII–[MoIV(CN)8]4- system leads to the construction of a novel coordination polymer [CuII(Me2en)][CuII(Me2en)2][MoIV(CN)8]·6H2O (1). The assembly reveals the unique structure consisting of 1–D chains constructed of {[Cu(Me2en)][Mo(CN)8]}n 2n- ladders with {[Cu(Me2en)2]2n+ pendant arms connected through cyanido–bridges to the Mo(IV) centers. Structural parameters of 1 were compared with other Cu(II)–Mo(IV) compounds with bidentate aliphatic polyamine ligands. Magnetic studies of 1 indicate paramagnetic behavior with weak antiferromagnetic interactions at low temperature. Photomagnetic studies with the application of 405, 473, 532 and 650 nm light sources and white light show no detectable photomagnetic effect. Conclusion: Novel 1–D ladder with pendant arms [CuII(Me2en)][CuII(Me2en)2][MoIV(CN)8]·6H2O (1) coordination polymer reveals unprecedented topological pattern and shows one of the highest complexities among 1–D octacyanidometallate– based chains. The local environments of metal centers were compared with other Cu(II)–Mo(IV) assemblies containing bidentate chelating polyamine ligands. In accordance with this analysis, two types of copper(II) moieties were distinguished among this kind of assemblies. Moreover, the analysis of [Mo(CN)8]4- for systems with various dimensionalities shows the same geometry and structural parameters of the moieties, differing in the number of bridging cyanides. Despite similar structural, spectroscopic and magnetic properties of 1 in comparison with other copper(II) complexes with aliphatic polyamines and octacyanidomolybdate(IV) revealing photomagnetic effect, no light induced increase of magnetization was observed. This leads to the observation that a large number of Cu(II)–NC–Mo(IV) linkages does not guarantee the presence of photomagnetic behavior.

Hydrolysis of imidazolidine ligands mediated by CuII: Mononuclear, tetranuclear and 1D CuII-amine complexes

The potential ability of HL1 [2-(1,3-dimethylimidazolidin-2-yl)phenol] and H3L2 [2,2′-(2-(2-hydroxyphenyl)imidazolidin-1,3-diyl)diethanol] to act as ligands towards copper(II) was tested under different reaction conditions. These essays show that both HL1 and H3L2 are unstable in the presence of CuII, suffering total imidazolidine ring hydrolysis and yielding amine complexes. In this way, four different copper(II) complexes could be isolated, depending on the reaction conditions, the ligand itself and the counterions present in the medium. Accordingly, the complexes [Cu(am1)(H2O)(OAc)2]n (1) (am1=N,N′-dimethylethylenediamine), [Cu(am1)(H2O)2(p-O2C-C6H4-CO2)]n (2), [Cu(am1)2(NO3)2] (3) and [Cu4(am2)2(OAc)8]·CH3CN·2H2O (4) (am2=N,N′-bis(2-hydroxyethyl)ethylenediamine) were obtained as the main products of the hydrolytic processes. The crystallographic characterisation of all of them shows great structural diversity. Thus, 1 is a mono-aqua bridged coordination polymer and 2 is a terephthalate bridged zig-zag chain, while 3 and 4 are discrete mononuclear and tetranuclear complexes, respectively. Magnetic characterisation of 1, 2 and 4 reveals different behaviours, with magnetic exchanges varying from weak ferromagnetic (2) to quite strong antiferromagnetic (4). The magnetic study of 1 is remarkable, as it constitutes, as far as we know, the first mono-aqua bridged copper(II) chain magnetically analysed, being an antiferromagnetic system.

Two novel metal–organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

Two 2-(1-imidazole)-1-hydroxyl-1,1׳-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H2en)[Co3(H2zdn)2(ox)(H2O)2] (1) and Cd2(H2zdn)(ox)0.5(H2O) (2) (2-(1-imidazole)-1-hydroxyl-1,1׳-ethylidenediphosphonic acid=H5zdn; oxalic acid=H2ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O–P–O units of H5zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property.

The role of steric constraints in the formation of rare aqua bridged coordination polymers: Synthesis, characterization and X-ray structures of polymeric, [Cu(2-chlorobenzoate)2(β-picoline)2(μ-H2O)]n and monomeric, [Cu(2-chlorobenzoate)2(γ-picoline)2(H2O)

Reaction of hydrated copper(II) 2-chloro-benzoate with β-/γ-picoline in methanol: water mixture (4:1 v/v) yielded polymeric [Cu(2-chlorobenzoate)2(β-picoline)2(μ-H2O)]n; 1 and monomeric [Cu(2-chlorobenzoate)2(γ-picoline)2(H2O)]; 2. The newly synthesized complexes have been characterized by elemental analyses, FT-IR spectroscopy, UV–Visible spectroscopy, TGA and single crystal X-ray structure determination. X-ray crystallographic analysis revealed that both complexes crystallize in the monoclinic crystal system with space group and unit cell dimensions: C2/c; a=51.71Å, b=10.58Å, c=10.02Å and β=100.5° for 1 and P21/c; a=11.81Å, b=16.33Å, c=13.79Å and β=90.77° for 2. Whereas in 1 the presence of constituent and mediating water molecules running along a-axis gives rise to 1-dimensional zig-zag polymer chains, in complex 2, the presence of square pyramidal arrangement of ligands around copper(II) center results in monomeric structure. Various non-covalent interactions like OH⋯O, CH⋯O and CH⋯л have been observed to play a decisive role in the stabilization of crystal lattices in both complexes.

Muconate bridged coordination polymers of Cu(II): Effect of auxiliary ligand on their structural architectures

Two coordination polymers [Cu2(2,2′-bpy)2(muco)2(H2O)2](H2O)2, (1) and [Cu(4,4′-bpy)(muco)(H2O)2], (2) [H2muco=trans,trans-muconic acid or 1,3-butadiene-1,4-dicarboxylic acid, 2,2′-bpy=2,2′-bipyridyl and 4,4′-bpy=4,4′-bipyridyl] have been synthesized by the reaction of muconate dianion with Cu(NO3)2·3H2O in presence of auxiliary ligands 2,2′-bpy and 4,4′-bpy respectively. Single crystal X-ray crystallographic structure determination reveals that 1 has one-dimensional (1D) structural motif and an extensive H-bonding pattern gives rise to 3D supramolecular network in the crystal of 1. On the contrary, 2 exhibits threefold interpenetrating three-dimensional (3D) net-work with CdSO4 topology. In the formation of these complexes, the auxiliary ligand has a vital role in directing the solid-state structure with defined topological network.