Two new supermolecular structures of organic-inorganic hybrid compounds: [Zn(phen)(SO4)(H2O)2]n and [Cu(phen)(H2O)2] · SO4 (phen = 1,10-phenanthroline)

Two new organic-inorganic hybrid compounds [Zn(phen)(SO₄)(H₂O)₂]_n (1) and [Cu(phen)(H₂O)₂] · SO₄ (2) have been prepared by conventional aqueous solution synthesis and characterized by single-crystal X-ray diffraction, IR spectroscopy, thermal gravimetric analysis (TGA) and fluorescent spectroscopy. In compound 1, the sulfate group adopts bidentate mode to coordinate with two Zn(II) ions to form one-dimensional polymer. The one-dimensional polymers are further linked together via the intermolecular hydrogen-bonding and π-π stacking interactions to form a 3D supramolecular framework. Compound 2 is build up of discrete [Cu(phen)(H₂O]²⁺ cations and SO₄²⁻ anions to form a three-dimensional framework via hydrogen-bonding and π-π stacking interactions. Furthermore, the luminescent properties of both 1 and 2 were studied. The complexes 1 and 2 excited at 280 nm wavelength produced characteristic luminescence features, arising maybe due to the π-π transitions.     

3D hydrogen bonded metal-organic frameworks constructed from [M(H2O)6][M′(dipicolinate)2] · mH2O (M/M′ = Zn/Ni or Ni/Ni). Identification of intercalated acyclic (H2O)6/(H2O)10 clusters

New heterodinuclear Zn^II/Ni^II (1) and homodinuclear Ni^II/Ni^II (2) water-soluble and air stable compounds of general formula [M(H₂O)₆][M′(dipic)₂] · mH₂O have been easily prepared by self-assembly of the corresponding metal(II) nitrates with dipicolinic acid (H₂dipic) in water solution at room temperature.  The compounds have been characterized by IR, UV/Vis and atomic absorption spectroscopies, elemental and X-ray single crystal diffraction (for 1 · 4H₂O and 2 · 5H₂O) analyses.  3D infinite polymeric networks are formed via extensive hydrogen bonding interactions involving all coordinated and crystallization water molecules, and all dipicolinate oxygens, thus contributing to additional stabilization of dimeric units, metal-organic chains and 2D layers.  In 1 · 4H₂O, the latter represent a rectangular-grid 2D framework with multiple channels if viewed along the c crystallographic axis, while in 2 · 5H₂O intercalated crystallization water molecules are associated to form acyclic nonplanar hexameric water clusters and water dimers which occupy voids in the host metal-organic matrix, with a structure stabilizing effect via host-guest interactions.  The hexameric cluster extends to the larger (H₂O)₁₀ one with an unusual geometry (acyclic helical octamer with two pendent water molecules) by taking into account the hydrogen bonds to water ligands in [Ni(H₂O)₆]²⁺.  The obtained Zn/Ni compound 1 relates to the recently reported family of heterodimetallic complexes [M(H₂O)₅M′(dipic)₂] · mH₂O (M/M′ = Cu/Co, Cu/Ni, Cu/Zn, Zn/Co, Ni/Co, m = 2, 3), what now allows to establish the orders of the metal affinity towards the formation of chelates with dipicolinic acid (Co^II > Ni^II > Zn^II > Cu^II) or aqua species (Co^II < Ni^II < Zn^II < Cu^II).     

Cobalt(II) and nickel(II) coordination polymers constructed from P,P′-diphenylmethylenediphosphinic acid (H2pcp) and 4,4′-bipyridine (bipy): Structural isomerism in [Co(pcp)(bipy)0.5(H2O)2]

The P,P′diphenylmethylenediphosphinic acid (H₂pcp) reacts with Co(ClO₄)₂ · 6H₂O and 4,4′-bipyridine to give a mixture of two polymeric isomers of formula [Co(pcp)(bipy)_0.5(H₂O)₂], {red (1) and pink (2)} and the new violet hybrid [Co(Hpcp)₂] (3). The pure red and violet species have been obtained by the reaction of H₂pcp with Co(CH₃COO)₂ · 4H₂O and bipy or with Co(ClO₄)₂ · 6H₂O, respectively. The analogous reaction of Ni(CH₃COO)₂ · 4H₂O or Ni(ClO₄)₂ · 6H₂O with H₂pcp and bipy affords only the [Ni(pcp)(bipy)_0.5(H₂O)₂] species (4). The two cobalt isomers present different structural arrangements. Whereas the red isomer (1) shows an undulated 2D layered structure, the pink one (2) forms an infinite monodimensional strand. Both the architectures extend to higher dimensions through hydrogen bonding interactions. The nickel derivative is isomorphous with the red cobalt isomer. The violet [Co(Hpcp)₂] (3), which is isomorphous with the complexes of the reported series [M(Hpcp)₂], M = Ca(II), Mg(II), presents a monodimensional polymeric structure. Compounds 1 and 4 show a very similar thermal behaviour, the two water molecules being lost in the temperature range 25-150 and 160-320 °C, respectively. Temperature dependent X-ray powder diffractometry (TDXD) has been performed on compound 1 in order to follow the structural transformations that occur during the heating process.     

Thiodiacetato-copper(II) chelates with or without N-heterocyclic donor ligands: molecular and/or crystal structures of [Cu(tda)]n, [Cu(tda)(Him)2(H2O)] and [Cu(tda)(5Mphen)] · 2H2O (Him = imidazole, 5Mphen = 5-methyl-1,10-phenanthroline)

Three new thiodiacetato-Cu(II) chelates have been synthesized and studied by X-ray crystallography and by thermal, spectral and magnetic methods. [Cu(tda)]_n (1) is a 3D-polymer with a pentadentate tda, which acts with a fac-O₂ + S(apical)-tridentate chelating conformation and as a twofold anti, syn-μ-η¹:η¹ carboxylate bridge. In its square pyramidal Cu(II) coordination (type 4 + 1) four O(carboxylate) donors define a close regular square base, but the Cu-S(apical) bond deviates 27.4° from the perpendicular to the mean basal plane. Each anti,syn-bridging carboxylate group exhibits two C-O (average 1.26(1) Å) and two Cu-O bonds (average 1.958(7) Å), which are very similar in length to each other. In contrast, the mixed-ligand complexes of [Cu(tda)(Him)₂(H₂O)] (compound 2, distorted octahedral, type 4 + 1 + 1) and [Cu(tda)(5Mphen)] · 2H₂O (compound 3, distorted square pyramidal, type 4 + 1) have molecular structures and the tda ligand displays only a fac-O₂ + S(apical)-tridentate conformation. The Cu-S(apical) bond lengths (2.570(1), 2.623(1) or 2.573(1) Å for 1, 2 or 3, respectively) are shorter than those previously reported for closely related Cu(II)-tda derivatives. The different tda ligand roles in their Cu(II) derivatives are rationalized on the basis of crystal packing forces driving in the absence or presence of auxiliary ligands (with two or three N-donor atoms).     

Three new multidimensional organic-inorganic hybrids based on polyoxometalates and copper coordination polymers with 4,4′-bipyridine ligands

Three new organic-inorganic hybrid materials with 4,4′-bipy ligands and copper cations as linkers, [Cu^II(H₂O)(4,4′-bipy)₂][Cu^II(H₂O)(4,4′-bpy)₂]₂H[Cu^IIP₈Mo₁₂O₆₂H₁₂] · 5H₂O (1), [Cu^I(4,4′-bipy)][Cu^II(4,4′-bipy)]₂ (BW₁₂O₄₀) · (4,4′-bipy) · 2H₂O (2) and [Cu^I (4,4′-bipy)]₃ (PMo₁₂O₄₀) · (pip) · 2H₂O (3) (pip = piperazine; 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. The single X-ray structural analysis reveals that the structure of 1 is constructed from [Cu(H₂O)(4,4′-bipy)₂] complexes into a novel, three-dimensional supermolecular network with 1-D channels in which Cu[P₄Mo₆]₂ dimer clusters reside. To the best of our knowledge, compound 1 is the first complex in which the [P₄Mo₆] clusters have been used as a non-coordinating anionic template for the construction of a novel, three-dimensional supermolecular network. Compound 2 is constructed from the six-supported [BW₁₂O₄₀]⁵⁻ polyoxoanions and [Cu^I(4,4′-bipy)] and [Cu^II(4,4′-bipy)] groups into a novel, 3-D network. Compound 3 exhibits unusual 3-D supramolecular frameworks, which are constructed from tetrasupporting [PMo₁₂O₄₀]³⁻ clusters and [Cu^I (4,4′-bipy)_n] coordination polymer chains. The electrochemical properties of 2 and 3 have been investigated in detail.     

Hydrothermal syntheses, crystal structures and characterizations of three new copper coordination polymers

Three new copper complexes, [Cu^IICu^I(ip)(ipH)(4,4′-bipy)_3/2]_n (1), [Cu(ip)(4,4′-bipy)]_n · 3nH₂O (2), and [Cu(ipH)₂(4,4′-bipy)]_n (3), have been hydrothermally synthesized by the reaction of Cu(NO₃)₂ · 3H₂O with isophthalic acid (ipH₂) and 4,4′-bipyridine (4,4′-bipy) under different reaction conditions. Complex 1, a mixed-valence copper(I,II) complex, exhibits a 2-D interpenetrating grid framework, in which five-coordinated Cu^II and three-coordinated Cu^I environments are established. The oxidation states of center Cu atoms have been confirmed by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance spectra (EPR). Complex 2 features a 2-D box-like bilayer architecture, in which Cu^II atoms are linked by ip ligands to form a 1-D double-chain and the resulting chains are further strutted by the 4,4′-bipy ligands. In complex 3, two bridging 4,4′-bipy ligands and two terminal ipH ligands confine the Cu^II center in a square plane coordination geometry. The whole molecule of 3 was arranged into a 1-D linear chain structure. Additionally, the thermogravimetric analyses (TGA) for complexes 1-3 are also discussed in this paper.     

Syntheses and crystal structures of cyano-bridged cluster-metal layered coordination polymers [Cu(dien)]3[W4Te4(CN)12] · 9H2O and [Ni(en)(NH3)]3[W4Se4(CN)12] · 7.5H2O

Two new tetrahedral tungsten cyanide cluster compounds, [Cu(dien)]₃[W₄Te₄(CN)₁₂] · 9H₂O (1) (dien=diethylenetriamine) and [Ni(en)(NH₃)]₃[W₄Se₄(CN)₁₂] · 7.5H₂O (2) (en=ethylenediamine), were synthesized by treating aqueous solutions of the saltlike cluster compound K₆[W₄Te₄(CN)₁₂] · 5H₂O/K₆[W₄Se₄(CN)₁₂] · 6H₂O with copper(II)/nickel(II) chloride in aqueous ammonia containing dien/en. The cyano-bridged layered coordination polymeric compounds were characterized by single-crystal X-ray diffraction analysis: monoclinic, space group P2₁ for 1; trigonal, space group for 2. Structures of 1 and 2 consist of infinite neutral layers of cluster components {W₄Te₄(CN)₁₂}/{W₄Se₄(CN)₁₂} connected, one another by {Cu(dien)} or {Ni(en)(NH₃)} fragments, respectively.     

Construction of one-, two- and three-dimensional Cu(I) polymeric architectures containing bis(diphenylphosphino)acetylene and 4,4′-bipyridine linking ligands

One-dimensional {[Cu₂(dppa)₂(4,4′-bipy)(CH₃CN)₂](BF₄)₂ · 2CH₃CN}_n (1), two-dimensional {[Cu₂(dppa)(4,4′-bipy)₂(CH₃CN)₂](BF₄)₂ · 4CH₂Cl₂ · 4H₂O}_n (2) and three-dimensional {[Cu₂(dppa)(4,4′-bipy)₃](BF₄)₂ · 2CH₂Cl₂ · 3CH₃CN · 3H₂O}_n (3) polymeric complexes have been prepared by self-assembly of [Cu(MeCN)₄]BF₄, Ph₂PCCPPh₂ (dppa) and 4,4′-bipyridine (4,4′-bipy) in a 2:2:1, 1:1:1 and 2:2:3 molar ratio, respectively. The structures of 1-3, determined by an X-ray diffraction study, reveal a linear spring-like architecture for 1, a planar honeycomb grid for 2 and an interlocked adamantoid network for 3.     

A trinuclear copper(II) complex with 2,5-pyridine-dicarboxylato bridges - [Cu3(2,5-pydc)2(Me5dien)2(H2O)2(BF4)2] · H2O: Synthesis, crystal structure and magnetic properties

A trinuclear copper(II) complex, [Cu₃(2,5-pydc)₂(Me₅dien)₂(BF₄)₂(H₂O)₂] · H₂O 1, has been constructed from 2,5-pyridine-dicarboxylato bridges (2,5-pydc²⁻) and N,N,N′,N″,N″-pentamethyl-diethylenetriamine (Me₅dien) acting as a blocking ligand. The copper ions, within the centrosymmetric trinuclear cations, are connected by two 2,5-pydc²⁻ bridges, with an intramolecular Cu···Cu separation of 8.432 Å. The central copper ion exhibits an elongated octahedral geometry, with semicoordinated ions, while the terminal ones are pentacoordinated (distorted square-pyramidal geometry). The cryomagnetic investigation of 1 reveals an antiferromagnetic coupling of the copper(II) ions (J = −5.9 cm⁻¹, H = −JS_Cu1S_Cu2 − JS_Cu2S_Cu1a).     

Hydrothermal synthesis, crystal structures and photoluminescent properties of four cadmium(II) coordination polymers derived from diphenic acid and auxiliary ligands

Four novel metal coordination polymers, [Cd(dpa)(H₂O)]_n (1), [Cd(dpa)(2,2′-bipy)]_n (2), {[Cd₂(dpa)₂(4,4′-bipy)₃](4,4′-bipy)(H₂O)₂}_n (3) and [Cd(dpa)(bim)₂(H₂O)]}_n (4) (H₂dpa = 2,4′-biphenyl-dicarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine, bim = benzimidazole), have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses reveal that the 2,4′-diphenic acids acts as bridging ligands, exhibiting rich coordination modes to link metal ions: bis-monodentate, bidentate chelating, chelating/bridging, monoatomic bridging and monodentate modes. In addition, the luminescent properties for compound 1-4 are also investigated in this work.     

Ln2(O2CCH2PO3)2(H2O)3 · H2O (Ln = La, Pr, Nd, Sm): Layered lanthanide phosphonoacetates containing two-dimensional -Ln-O- linkages

Four novel isostructural lanthanide phosphonate compounds with formula Ln₂(O₂CCH₂PO₃)₂(H₂O)₃ · H₂O [Ln = La (1), Pr (2), Nd (3), Sm (4)] have been prepared through hydrothermal reactions of phosphonoacetate acid and lanthanide nitrates. All show layered structures made up of {LnO₉} polyhedra and {CPO₃} tetrahedra with the lattice water molecules locating between the layers. Within the layer, chains of edge-sharing {LnO₉} polyhedra are connected via corner-sharing by phosphonate oxygens forming a two-dimensional -Ln-O- linkage. Thermal analyses and XRD measurements reveal that the framework structures can be maintained up to 400 °C.     

Long-range superexchanged magnetic interaction observed in heterometallic complex: {[Fe(Tpms)(CN)3][Mn(H2O)2(DMF)2]} · DMF

A new tri-cyanometalate building block for heterometallic complexes, [PPh₄]₂[Fe^II(Tpms)(CN)₃] (2) (PPh₄ = tetraphenylphosphonium; Tpms = tris(pyrazolyl) methanesulfonate), has been prepared. Using it as a building block, a one-dimensional chain compound, {[Fe^II(Tpms)(CN)₃][Mn^II(H₂O)₂( DMF)₂]} · DMF (3), has been synthesized and structurally characterized. The magnetic properties of 3 correspond to a ferromagnetic chain with weak long-range superexchanged magnetic interaction between the high-spin manganese(II) ions.     

Synthesis, characterization, crystal structures and magnetic properties of dissymmetrical double schiff base heterotrinuclear complexes: [CuL(H2O)CoCuL] · H2O · CH3OH and [(CuL)2Ni] · 2H2O

A dissymmetrical double Schiff base Cu(II) mononuclear complex: CuHL (1) (where H₃L is N-3-carboxylsalicylidene-N^′-salicylaldehyde-1,2-diaminoethane) and two trinuclear complexes: [CuL(H₂O)CoCuL] · H₂O · CH₃OH (2) and [(CuL)₂Ni] · 2H₂O (3) have been synthesized and characterized by means of elemental analyses, IR and electronic spectra. The crystal structures of two heterotrinucler complexes were determined by X-ray analysis. Each dissymmetrical cell unit of the complex 2 contains two heterotrinucler neutral molecules. In each neutral molecule, the central Co²⁺ ion is located at the site of O₆ with a distorted octahedral geometry and one terminal Cu²⁺ ion at the four-coordination site of N₂O₂, but the other one at the square-pyramidal environment of N₂O₃. Each dissymmetrical unit of the complex 3 contains a heterotrinucler neutral molecule, whose structure is similar to that of 2 except two terminal Cu²⁺ ions both at the inner site of N₂O₂. The magnetic properties of two heterotrinucler complexes have been determined in the temperature range of 5-300 K, which indicate that the interaction between the central Co²⁺ ion or Ni²⁺ ion and the outer Cu²⁺ ions is antiferromagnetic. The exchange integrals are equal to −26.2 cm⁻¹ for 2 and −50.6 cm⁻¹ for 3.     

Syntheses, structures, and magnetic properties of three Fe(II) complexes with reduced radical ligands

Three new Fe(II) complexes [Fe(HIM2py)₂(SCN)₂] (1), [Fe(HIM2py)₂(H₂O)₂](ClO₄)₂ · 2H₂O (2), and [Fe(HIM2py)₂(4,4-bipy)](ClO₄)₂ · 3CH₃CH₂OH (3) (4,4-bipy = 4,4′-bipyridine, HIM2py = 1-hydroxyl-2(2′-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole) have been synthesized and characterized structurally as well as magnetically. The X-ray analysis reveals that HIM2py ligands are coordinated to the metal ions as an unusual six-membered didentate chelate with the κ²N(py), O(HIM) mode. Fe(II) ions in complex 3 are bridged by 4,4-bipy, leading to a 1D chain structure. The magnetic behavior of complex 3 is investigated, showing weak antiferromagnetic interactions.     

Reactivity of [Ru(pac)(H2O)] (pac = polyaminocarboxylate) complexes with 5′-nucleotides and their antitumor activity

The reaction of [Ru^III(edta)(H₂O)]⁻ (edta⁴⁻ = ethylenediaminetetraacetate) and [Ru^III(hedtra)(H₂O)] (hedtra³⁻ = N-hydroxyethylethylenediaminetriacetate) with various purine based 5′-nucleotides (Nu) viz. adenosin-5′-monophosphate (AMP), guanosin-5′-monophosphate (GMP), inosin-5′-monophosphate (IMP) was studied kinetically as a function of [Nu] at various temperatures (15-35 °C) at a fixed pH (4.5). Kinetic results suggest that the binding of 5′-nucleotides takes place in a rapid [Nu] dependent rate-determining step. Kinetic data and activation parameters are accounted for the operation of an associative mechanism. The antitumor activities of both [Ru^III(edta)(H₂O)]⁻ (1) and [Ru^III(hedtra)(H₂O] (2) have been evaluated using MCF-7 (breast cancer), NCI-H460 (lung cancer) and SF-268 (CNS) cell lines.     

Analysis of the main structural trends for biscyclometalated dinuclear rhodium compounds of general formula Rh2(O2CR)2(PC)2 · 2H2O

A new series of biscyclometalated dinuclear rhodium (II) compounds with the general formula Rh₂(O₂CR)₂(PC)₂ · 2H₂O, being PC = (C₆H₄)P(C₆H₅)₂, R = CH₃ (1 · 2H₂O), PC = [(p-CH₃ OC₆H₃)P(p-CH₃ OC₆H₄)₂], R = CF₃ (2 · 2H₂O), PC = (C₆H₄)P[CH(CH₃)₂]₂, R = CH₃ (3 · 2H₂O) and PC = (C₆H₄)P(C₆H₅)₂, R = C₆F₅ (4 · 2H₂O) has been obtained. The crystal structures for these compounds have been determined by X-ray diffraction and the main structural trends, bond lengths, bond angles and torsion angles have been analyzed, and have also been compared with the structural parameters for different analogous complexes described previously in the literature.     

Hybrid organic-inorganic assemblies built up from saturated heteropolyoxoanions and copper coordination polymers with mixed 4,4′-bipyridine and 2,2′-bipyridine ligands

Three new organic-inorganic hybrid compounds [Cu^I(2,2′-bipy)(4,4′-bipy)_0.5]₂[Cu^I(2,2′-bipy)(4,4′-Hbipy)][Cu^I(4,4′-bipy)]₂[P₂W₁₈O₆₂] · 3H₂O (1), [Cu^I(2,2′-bipy)(4,4′-bipy)_0.5]₂[Cu^I(4,4′-bipy)]₂[PW₁₂O₄₀] · 0.25H₂O (2), and[Cu^I(4,4′-bipy)]₃[PMo₁₂O₄₀] · en · 3H₂O (3) (2,2′- bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. Compound 1 represents the first 1D ladderlike structure formed by Dawson-type polyoxoanion [P₂W₁₈O₆₂]⁶⁻ and coordination polymer with mixed 4,4′-bipy and 2,2′-bipy ligands. The novel structure of 2 is composed of 1D hybrid zigzag chains linked by chains into a 3D framework. In compound 3, the [PMo₁₂O₄₀]³⁻ clusters are hung on chains to form a new 1D chain.     

Robust anionic building blocks [M(malonate)2(H2O)2] for crystal engineering of inorganic-organic hybrid materials

One-pot reactions of transition metal (Cu^II, Ni^II, Co^II, or Cd^II) salt with malonic acid (H₂mal) in the presence of mesocyclic diamine generate three supramolecular complexes and a coordination polymer. [Cu(mal)₂(H₂O)₂](H₂O)₂(H₂DACH) (1) and [M(mal)₂(H₂O)₂](H₂DACO) (M = Ni for 2, and Co for 3) are ion-pair products and managed by charge-assistant noncovalent interactions (DACO = 1,5-diazacyclooctane, and DACH = 1,4-diazacycloheptane). In these structures, the similar mononuclear [M(mal)₂(H₂O)₂]²⁻ building blocks are connected by hydrogen bonds to form 2D networks (with the aid of one lattice water in the case of 1), which are further extended by the cationic diamine components to yield 3D pillar-layered solids. While [Cd(mal)(H₂O)₂]_n (4) is a neutral polymeric complex, in which the similar [Cd(mal)₂(H₂O)₂]²⁻ subunits are propagated by additional Cd-O coordinative forces to result in the final 2D layer.     

Three novel coordination networks dependent upon H2btze ligand [H2btze = 1,2-bis(tetrazol-5-yl) ethane]

Three novel metal-organic frameworks, [Zn(btze)]_n (1), [Zn(btze)(H₂O)]_n (2) and [Mn(btze)(H₂O)₄]_n·(H₂O)₂ (3) [btze = 1,2-bis(tetrazol-5-yl) ethane anion], were synthesized and characterized by elemental analysis, IR spectroscopy, X-ray crystallography and thermogravimetric analysis. The crystal structures study reveal that 1 displays a 3D framework, 2 displays a 2D layer structure and 3 displays a 1D polymeric chain. The luminescence properties of 1-3 were investigated at room temperature in solid state.     

3D supramolecular network assembly and thermal decomposition of new copper(II) complexes with pyrazine-2,6-dicarboxylic acid

Four new Cu(II) complexes [Cu(pzda)(2,2′-bpy)(H₂O)] · 2.5H₂O (1), [Cu(pzda)(phen)(H₂O)] · H₂O (2), [Cu(pzda)(4,4′-bpy)] · H₂O (3) and [Cu(pzda)(bpe)_0.5(H₂O)] (4) were synthesized by hydrothermal reactions of copper salt (acetate or sulphate) with pyrazine-2,6-dicarboxylic acid (H₂pzda), and 2,2′-bipyridine (2,2′-bpy), 1,10-phenanthroline (phen), 4,4′-bipyridine (4,4′-bpy) or 1,2-bis(4-pyridyl)-ethane (bpe), respectively. For 1 and 2, they are both monomeric entities which are further assembled into 3D supramolecular networks by hydrogen bonds and π-π stacking interactions. Complex 3 has a 2D metal-organic framework which is connected into 3D supramolecular network by hydrogen bonds. However, for 4, the bpe ligand bridges two Cu(II) ions into binuclear unit, and then the binuclear molecules are assembled into 3D supramolecular network by hydrogen bonds between the coordination water molecule and the carboxylate oxygen atoms. The thermal decomposition mechanism of complexes 1 and 2 cooperated with powder XRD at different temperatures is discussed. The results reveal that once liberation of water molecules takes place the supramolecular network of 1 and 2 collapses.