CuII Ions Research Articles

Interaction of the potent antitumoral compounds Casiopeinas® with blood serum and cellular bioligands

Casiopeinas® are among the few CuII compounds patented for their antitumor activity, but their mode of action has not been fully elucidated yet. One of them, Cas II-gly, is formed by 4,7-dimethyl-1,10-phenanthroline (Me2phen) and glycinato (Gly). In blood and cells, Cas II-gly can keep its identity or form mixed species with serum or cytosol bioligands (bL or cL) with composition CuII–Me2phen–bL/cL, CuII–Gly–bL/cL, or CuII–bL/cL. In this study, the binding of Cas II-gly with low molecular mass bioligands of blood serum (citric, L-lactic acid, and L-histidine) and cytosol (reduced glutathione (GSH), reduced nicotinamide adenine dinucleotide (NADH), adenosine triphosphate (ATP), and l-ascorbic acid) was examined through the application of instrumental (ElectroSpray Ionization-Mass Spectrometry and Electron Paramagnetic Resonance) and computational (Density Functional Theory) methods. The results indicated that mixed species CuII–Me2phen–bL/cL are formed, with the bioligands replacing glycinato. The formation of these adducts may participate in the copper transport toward the target organs and facilitate the cellular uptake or, in constrast, preclude it. In the systems with GSH, NADH and L-ascorbate, a redox reaction occurs with the partial oxidation of cL to the corresponding oxidized form (GSSG, NAD+ and dehydroascorbate) which interact with CuII. Formed CuI ion does not give complexation reactions with reduced or oxidized form of bioligands for its ‘soft’ character and low affinity for oxygen and nitrogen donors compared to CuII. However, CuI could promote Fenton-like reactions with production of reactive oxygen species (ROS) related to the antitumor activity of Casiopeinas®.

The Copper Chaperone NosL Forms a Heterometal Site for Cu Delivery to Nitrous Oxide Reductase.

The final step of denitrification is the reduction of nitrous oxide (N2O) to N2, mediated by Cu‐dependent nitrous oxide reductase (N2OR). Its metal centers, CuA and CuZ, are assembled through sequential provision of twelve CuI ions by a metallochaperone that forms part of a nos gene cluster encoding the enzyme and its accessory factors. The chaperone is the nosL gene product, an 18 kDa lipoprotein predicted to reside in the outer membrane of Gram‐negative bacteria. In order to better understand the assembly of N2OR, we have produced NosL from Shewanella denitrificans and determined the structure of the metal‐loaded chaperone by X‐ray crystallography. The protein assembled a heterodinuclear metal site consisting of ZnII and CuI, as evidenced by anomalous X‐ray scattering. While only CuI is delivered to the enzyme, the stabilizing presence of ZnII is essential for the functionality and structural integrity of the chaperone.

Loading Linear Arrays of CuII Inside Aromatic Amide Helices.

The very stable helices of 8‐amino‐2‐quinolinecarboxylic acid oligoamides are shown to uptake CuII ions in their cavity through deprotonation of their amide functions with minimal alteration of their shape, unlike most metallo‐organic structures which generally differ from their organic precursors. The outcome is the formation of intramolecular linear arrays of a defined number of CuII centers (up to sixteen in this study) at a 3 Å distance, forming a molecular mimic of a metal wire completely surrounded by an organic sheath. The helices pack in the solid state so that the arrays of CuII extend intermolecularly. Conductive‐AFM and cyclic voltammetry suggest that electrons are transported throughout the metal‐loaded helices in contrast with hole transport observed for analogous foldamers devoid of metal ions.

Loading Linear Arrays of CuII Inside Aromatic Amide Helices

AbstractThe very stable helices of 8‐amino‐2‐quinolinecarboxylic acid oligoamides are shown to uptake CuII ions in their cavity through deprotonation of their amide functions with minimal alteration of their shape, unlike most metallo‐organic structures which generally differ from their organic precursors. The outcome is the formation of intramolecular linear arrays of a defined number of CuII centers (up to sixteen in this study) at a 3 Å distance, forming a molecular mimic of a metal wire completely surrounded by an organic sheath. The helices pack in the solid state so that the arrays of CuII extend intermolecularly. Conductive‐AFM and cyclic voltammetry suggest that electrons are transported throughout the metal‐loaded helices in contrast with hole transport observed for analogous foldamers devoid of metal ions.

Benchmark C2 H2 /CO2 Separation in an Ultra-Microporous Metal-Organic Framework via Copper(I)-Alkynyl Chemistry.

Separation of acetylene from carbon dioxide remains a daunting challenge because of their very similar molecular sizes and physical properties. We herein report the first example of using copper(I)-alkynyl chemistry within an ultra-microporous MOF (CuI @UiO-66-(COOH)2 ) to achieve ultrahigh C2 H2 /CO2 separation selectivity. The anchored CuI ions on the pore surfaces can specifically and strongly interact with C2 H2 molecule through copper(I)-alkynyl π-complexation and thus rapidly adsorb large amount of C2 H2 at low-pressure region, while effectively reduce CO2 uptake due to the small pore sizes. This material thus exhibits the record high C2 H2 /CO2 selectivity of 185 at ambient conditions, significantly higher than the previous benchmark ZJU-74a (36.5) and ATC-Cu (53.6). Theoretical calculations reveal that the unique π-complexation between CuI and C2 H2 mainly contributes to the ultra-strong C2 H2 binding affinity and record selectivity. The exceptional separation performance was evidenced by breakthrough experiments for C2 H2 /CO2 gas mixtures. This work suggests a new perspective to functionalizing MOFs with copper(I)-alkynyl chemistry for highly selective separation of C2 H2 over CO2 .

Two-Dimensional Nitronyl Nitroxide–Cu Networks Based on Multi-Dentate Nitronyl Nitroxides: Structures and Magnetic Properties

Two multi-dentate nitronyl nitroxide radicals, namely, bisNITPhPy ([5-(4-pyridyl)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)]benzene) and NIT-3Py-5-4Py (2-{3-[5-(4-pyridyl)]pyridyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were assembled with CuII ions to obtain two-dimensional heterospin 2p–3d coordination polymers [Cu7(hfac)14(bisNITPhPy)2]n (1) and [Cu2(hfac)4(NIT-3Py-5-4Py)]n (2) (hfac: hexafluoroacetylacetonate). In both compounds, the bisNITPhPy and NIT-3Py-5-3Py radicals acted as pentadentate and tetradentate ligands, respectively, to connect with CuII ions, generating a 2D layer structure. The analysis of the magnetic behavior indicated that strong antiferromagnetic coupling and ferromagnetic interaction (J = 17.1 cm−1) coexisted in 1. For 2, there were ferromagnetic couplings between the CuII ion and NO group, as well as the CuII ion and radical via the pyridine ring with J1 = 32.8 and J2 = 2.2 cm−1, respectively.

Oxidase Reactivity of CuII Bound to N-Truncated Aβ Peptides Promoted by Dopamine.

The redox chemistry of copper(II) is strongly modulated by the coordination to amyloid-β peptides and by the stability of the resulting complexes. Amino-terminal copper and nickel binding motifs (ATCUN) identified in truncated Aβ sequences starting with Phe4 show very high affinity for copper(II) ions. Herein, we study the oxidase activity of [Cu–Aβ4−x] and [Cu–Aβ1−x] complexes toward dopamine and other catechols. The results show that the CuII–ATCUN site is not redox-inert; the reduction of the metal is induced by coordination of catechol to the metal and occurs through an inner sphere reaction. The generation of a ternary [CuII–Aβ–catechol] species determines the efficiency of the oxidation, although the reaction rate is ruled by reoxidation of the CuI complex. In addition to the N-terminal coordination site, the two vicinal histidines, His13 and His14, provide a second Cu-binding motif. Catechol oxidation studies together with structural insight from the mixed dinuclear complexes Ni/Cu–Aβ4−x reveal that the His-tandem is able to bind CuII ions independently of the ATCUN site, but the N-terminal metal complexation reduces the conformational mobility of the peptide chain, preventing the binding and oxidative reactivity toward catechol of CuII bound to the secondary site.

Measurement of Interpeptidic CuII Exchange Rate Constants of CuII-Amyloid-β Complexes to Small Peptide Motifs by Tryptophan Fluorescence Quenching.

The interpeptidic CuII exchange rate constants were measured for two Cu amyloid-β complexes, Cu(Aβ1-16) and Cu(Aβ1-28), to fluorescent peptides GHW and DAHW using a quantitative tryptophan fluorescence quenching methodology. The second-order rate constants were determined at three pH values (6.8, 7.4, and 8.7) important to the two Cu(Aβ) coordination complexes, components Cu(Aβ)I and Cu(Aβ)II. The interpeptidic CuII exchange rate constant is approximately 104 M-1 s-1 but varies in magnitude depending on many variables. These include pH, length of the Aβ peptide, location of the anchoring histidine ligand in the fluorescent peptide, number of amide deprotonations required in the tryptophan peptide to coordinate CuII, and interconversion between Cu(Aβ)I and Cu(Aβ)II. We also present EPR data probing the CuII exchange between peptides and the formation of ternary species between Cu(Aβ) and GHW. As the nonfluorescent GHK and DAHK peptides are important motifs found in the blood and serum, their ability to sequester CuII ions from Cu(Aβ) complexes may be relevant for the metal homeostasis and its implication in Alzheimer's disease. Thus, their kinetic CuII interpeptidic exchange rate constants are important chemical rate constants that can help elucidate the complex CuII trafficking puzzle in the synaptic cleft.

A mixed-valence CuII/CuI coordination polymer based on bridged thiocyanate and in situ formed di(N-heterocyclic) sulfide: Synthesis, structure, and magnetic properties

A mixed-valence CuII/CuI coordination polymer {CuIICuI2[S(PIP)2](μ-SCN)4}n (1) has been generated via the reaction of KSCN, CuCl2·2H2O, and 3-(pyridin-2-yl)imidazo[1,5-a]pyridine (HPIP) under solvothermal conditions. The di(N-heterocyclic) sulfide ligand [S(PIP)2] (S(PIP)2 = bis(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)sulfane) was formed in situ by the reaction of HPIP and KSCN in the presence of CuCl2·2H2O. The structure of compound 1 was determined by X-ray single crystal diffraction. In the structure of 1, one CuII ion, which is chelated by one neutral [S(PIP)2] ligand, and two CuI ions are connected by end-to-end thiocyanates to generate an infinite 2D coordination polymer. Complex 1 was also characterized by IR, PXRD, XPS and ESR. The magnetic properties of 1 have been investigated.

1,4,7‐Triazacyclononane (tacn) with N,N′‐bridging methylene‐bis(phosphinic acid) group and its complexes

AbstractA bicyclic ligand, 1,4,7‐triazacyclononane 1,4‐bridged with methylene‐bis(phosphinate) and bearing benzyl substituent on the remaining amino group, was synthesized from N‐benzyl‐tacn and CH2(PO2H2)2 by two sequential Mannich‐type reactions in a high yield. Basicity of the macrocycle is high (pK1=12.25). Complexes with CuII and NiII ions show dimeric structures in the solid state. The structures exhibit distorted octahedral environment with two ring amino groups from one molecule and two oxygen atoms of chelating bis(phosphinate) anion from the other molecule in the equatorial plane, and with the apical positions occupied by the remaining macrocycle amino group and by one of the phosphinate oxygen atoms. The metal ions in the dimers are additionally bridged by one phosphinate group. Stability of the CuII complex is more than ten orders of magnitude lower than that of the [Cu(nota)]− complex due to a different number and different nature of the pendant arms, and inappropriate arrangement of donor atoms in the ligand bicyclic structure. Rigidity of the short P−C−P chain of the geminal methylene‐bis(phosphinate) does not allow simultaneous coordination of both phosphinate groups and the ring amines to the same metal ion. The low solubility of NiII and ZnII complexes disabled determination of their stability constants.

Synthesis, structure and computational study of 5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine (Pesta) and its heterometallic π,σ-complex [Cu2FeCl2(Pesta)4][FeCl4

Copper(I) π-coordination compounds with allyl derivatives of azoles are an interesting subject of current research, but CuI π-complexes with other transition-metal ions incorporated in the structure have been virtually uninvestigated. The present work is directed toward the synthesis and structural characterization of the novel heterometallic CuI/FeII π-complex di-μ2-chlorido-1:2κ2Cl;2:3κ2Cl-tetrakis[μ2-5-(prop-2-en-1-ylsulfanyl)-1,3,4-thiadiazol-2-amine]-1:2κ2N4:N3;1(η2),κN4:2κN3;2:3κ2N3:N4;2κN3:3(η2),κN4-dicopper(I)iron(II) tetrachloridoferrate(II), [Cu2FeCl2(C5H7N3S2)4][FeCl4] (1). The structure of the 5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine (Pesta, C5H7N3S2) ligand is also presented. The cationic substructure in 1 consists of one FeII and two CuI ions bridged by two chloride ions along with two σ,σ- and two π,σ-coordinated ligands, whereas the anionic part is built of isolated tetrahedral [FeCl4]2- ions. π-Coordination of the Pesta allyl group to the CuI ions prevents agglomeration of the inorganic Cu-Cl-Fe-Cl-Cu part into infinate chains. An energy framework computational analysis was performed for Pesta.

Study of interaction of metal ions with methylthymol blue by chemometrics and quantum chemical calculations

In this study, we determine the acidity constants of methylthymol blue (MTB) and association constants of its complexes with the ZnII, CuII, and FeII metal ions (MIs), through theoretical and experimental means. The complexes were characterized using UV–Visible absorption spectroscopy combined with soft/hard chemometrics methods and quantum chemical calculations. Quantum chemical calculations revealed that electronic transitions in the UV–Visible spectra of MTB have mixed n → π* and π → π* characters. The results of molar ratio and multivariate curve resolution alternating least squares (MCR-ALS) revealed the formation of successive 1:2 and 1:1 complexes (MI:MTB) for the ZnII and CuII systems. However, the formation of successive 1:1 and 2:1 complexes are suggested for FeII by the molar ratio and MCR-ALS. The majority of transitions observed in the UV–Visible spectra of the Zn(MTB) and Cu(MTB) complexes have ligand-to-ligand charge transfer (LLCT) characters. However, the transitions in the UV–Visible spectrum of the Fe(MTB) complex have LLCT and metal-to-ligand charge transfer (MLCT) characters. For the Fe2(MTB) complex, the lowest energy transition of has an LLCT character. However, its higher energy transitions are a mixture of LLCT, MLCT, and metal-to-metal charge transfer (MMCT) characters. The correlation between experimental and computed wavelengths revealed that the 1:1 complexes of ZnII and CuII prefer square pyramidal geometries. However, the FeII complexes always show octahedral geometry.

Ligand Induced CuII Transport Restricts Cancer and Mycobacterial Growth: Towards a Plug-and-Select Ion Channel Scaffold.

Synthetic channels with high ion selectivity are attractive drug targets for diseases involving ion dysregulation. Achieving selective transport of divalent ions is highly challenging due their high hydration energies. A small tripeptide amphiphilic scaffold installed with a pybox ligand selectively transports CuII ions across membranes. The peptide forms stable dimeric pores in the membrane and transports ions by a Cu2+ /H+ antiport mechanism. The ligand-induced excellent CuII selectivity as well as high membrane permeability of the peptide is exploited to promote cancer cell death. The peptide's ability to restrict mycobacterial growth serves as seeds to evolve antibacterial strategies centred on selectively modulating ion homeostasis in pathogens. This simple peptide can potentially function as a universal, yet versatile, scaffold wherein the ion selectivity can be precisely controlled by modifying the ligand at the C terminus.

Insight into Rare Structurally Characterized Homotrinuclear CuII Non-Symmetric Salamo-Based Complex

A rare homotrinuclear CuII salamo-based complex [Cu3(L)2(μ-OAc)2(H2O)2]·2CHCl3·5H2O was prepared through the reaction of a non-symmetric salamo-based ligand H2L and Cu(OAc)2·H2O, and validated by elemental analyses, UV-Visible absorption, fluorescence and infrared spectra, molecular simulation and single-crystal X-ray analysis techniques. It is shown that three CuII atoms and two wholly deprotonated ligand (L)2− moieties form together a trinuclear 3:2 (M:L) complex with two coordination water molecules and two bi-dentate briging μ-acetate groups (μ-OAc−). Besides, the Hirshfeld surface analysis of the CuII complex was investigated. Compared with other ligands, the fluorescent strength of the CuII complex was evidently lowered, showing that the CuII ions possess fluorescent quenching effect.

Synthesis, crystallographic characterization and Hirshfeld surface analysis of metal complexes of conformationally constrained β-amino acid, 2-(1-aminocyclohexyl)acetic acid with CoII, NiII, CuII and ZnII ions

2-(1-aminocyclohexyl)acetic acid (β 3,3-Ac6cH) is selected as a lead compound to synthesize a new series of mononuclear transition metal complexes of the type [MII-(Κ2-O,N- β 3,3-Ac6c)2(H2O)2] (M = CoIIC1, NiIIC2, CuIIC3, and ZnIIC4. All the complexes C1-C4 have been suitably characterized by relevant spectroscopic techniques, viz. NMR (1H, 13C, DEPT 135), UV–visible, IR, and HRMS (for C1) spectroscopies. These complexes displayed ν(M-N) and ν(M-O) bands in the region of 417–448 and 395–410 cm−1, respectively having maximum absorbance in the UV region. A clear blue shifts up to 20–51 nm of n→π* electronic transition band (360–390 nm), compared to its position in β3,3-Ac6cH, clearly demonstrates the participation of amine/carboxylate moieties in the complex formation. In addition, complexes C1, C2, and C3 exhibit weak d-d transition bands in the visible region at 560 nm, 630 nm, and 602 nm, respectively. The X-ray analysis of both complexes C3 and C4 confirms the distorted octahedral geometry around Cu and Zn centers. In both complexes, the equatorial positions are occupied by N, O donor sites of coordinated ligands, while the axial positions are occupied by oxygen atoms of the two water molecules. The molecules of C3 and C4 are predominantly stabilized by several intermolecular bifurcated non-conventional hydrogen bonding interactions, viz. NH…O, and OH…O in the solid state. Notably, the space fill model demonstrates the formation of rectangular voids in the molecular packing of C3, showing 2D sheet like architecture in ab-plane. The Hirshfeld surface and subsequent fingerprint plots were calculated to quantify the intermolecular contacts present within the crystal structure of compounds C3 and C4.

DNA Binding and DNA Cleavage Activities of Newly Synthesized Co

Two water soluble complexes with CoII and CuII ions were synthesized using a novel β-cyclodextrin based azo-functionalized Schiff base as a ligand. The Schiff base and its metal complexes were characterized by different physico-chemical and spectroscopic methods. From the analyses of the experimental data, distorted octahedral geometry has been assigned for both the metal complexes. The binding interactions between the metal complexes and DNA were investigated by means of a thermal denaturation study and viscosity measurements as well as by electronic absorption and fluorescence spectroscopy. The DNA cleavage efficacy of the metal complexes was also studied by agarose gel electrophoresis using pBR DNA. These studies revealed that both the metal complexes followed an intercalative mode of binding to calf thymus (CT)-DNA and also effectively cleaved the supercoiled pBR DNA. The CoII complex, however, more efficiently cleaved CT-DNA than the CuII complex as much as the experimental results are concerned.

In situ X-ray absorption study of Cu species in Cu-CHA catalysts for NH3-SCR during temperature-programmed reduction in NO/NH3

Ammonia-mediated selective catalytic reduction (NH3-SCR) using Cu-exchanged chabazite zeolites as catalysts is one of the leading technologies for NOx removal from exhaust gases, with CuII/CuI redox cycles being the basis of the catalytic reaction. The amount of CuII ions reduced by NO/NH3 can be quantified by the consumption of NO during temperature-programmed reduction experiments (NO-TPR). In this article, we show the capabilities of in situ X-ray absorption near-edge spectroscopy (XANES), coupled with multivariate curve resolution (MCR) and principal component analysis (PCA) methods, in following CuII/CuI speciation during reduction in NO/NH3 after oxidation in NO/O2 at 50 °C on samples with different copper loading and pretreatment conditions. Our XANES results show that during the NO/NH3 ramp CuII ions are fully reduced to CuI in the 50–290 °C range. The number of species involved in the process, their XANES spectra and their concentration profiles as a function of the temperature were obtained by MCR and PCA. Mixed ligand ammonia solvated complexes [CuII(NH3)3(X)]+ (X = OH−/O− or NO3−) are present at the beginning of the experiment, and are transformed into mobile [CuI(NH3)2]+ complexes: these complexes lose an NH3 ligand and become framework-coordinated above 200 °C. In the process, multiple CuII/CuI reduction events are observed: the first one around 130 °C is identified with the reduction of [CuII(NH3)3(OH/O)]+ moieties, while the second one occurs around 220–240 °C and is associated with the reduction of the ammonia-solvated Cu-NO3− species. The nitrate concentration in the catalysts is found to be dependent on the zeolite Cu loading and on the applied pretreatment conditions. Ammonia solvation increases the number of CuII sites available for the formation of nitrates, as confirmed by infrared spectroscopy.

Synthesis, crystal structures, fluorescence, and magnetic properties of 1,3,5-benzenetricarboxylate coordination polymers

Four new coordination polymers, {[Mn3(BTC)2(4-pp)6(H2O)2]·(4-pp)2(H2O)2}n 1, [Cu3(BTC)2(dpa)2]n 2, {[Zn3(BTC)2(4-pp)6]·(H2O)}n 3, and [Ag2(HBTC)(Pz)1/2]n 4, were synthesized under pH-controlled solvothermal conditions with symmetrical polycarboxylic acid of 1,3,5-benzenetricarboxylic acid (H3BTC) and nitrogen-containing heterocyclic compounds, pyrazine (pz), 4-phenylpyridine (4-pp), and 4,4′-dipyridylamine (dpa). Complexes 1–4 were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction, thermal gravimetric analysis, photoluminescence, and magnetic susceptibility. Complexes 1 and 3 show two-dimensional (2-D) layered structures, 2 exhibits a three-dimensional (3-D) network structure, and 4 is a one-dimensional (1-D) polymeric chain structure. Magnetic susceptibility measurements indicate that 1 shows weak antiferromagnetic coupling between MnII ions and 2 exhibits ferromagnetic interaction between CuII ions. The photoluminescence properties of 3 and 4 are similar to the ligand H3BTC.

AN NOVEL ANTIBACTERIAL ACTIVE [CuII–GdIII] COMPLEX CONSTRUCTED FROM AN ASYMMETRIC SALAMO-BASED LIGAND: SYNTHESIS AND STRUCTURAL CHARACTERIZATION

In the present study, we describe a reaction of Cu(OAc)2·H2O and Gd(NO3)3·6H2O with equimolar amounts of the asymmetric salamo-type ligand 6-methoxy-6′-ethoxy-2,2′-[ethylenedioxybis(azinomethyl)]diphenol (H2L) generated by Schiff base condensation of 2-[O-(1-ethyloxyamide)]oxime-3-methoxy-phenol with 3-ethoxysalicylaldehyde to obtain a novel 3d–4f hetero-polynuclear complex [{Cu(L)Gd(NO3)3}2] [Cu(L)Gd(NO3)3]2. The complex is fully characterized by X-ray diffraction (XRD), elemental analyses, FTIR and UV-Vis spectra. The phase purity is clearly confirmed by powder XRD. In the [CuII–GdIII] complex, the coordination environments of CuII ions are different, but the apical coordination atoms to the GdIII ions are nearly identical. The antibacterial and fluorescent properties of the H2L ligand and the [CuII–GdIII] complex are also investigated. Supramolecular interactions are studied in detail.

Synthesis, structural characterization, fluorescence properties, and DFT calculations of a novel hetero-hexanuclear [CuII 4GdIII 2] bis(salamo)-like complex involving bidentate chelating and bridging nitrate groups

A novel hetero-hexanuclear [CuII 4GdIII 2] complex with a symmetrical bis(salamo)-like tetraoxime ligand (H4L), [{Cu2(L)(MeOH)Gd(NO3)2(μ 2-NO3)}2]·2CH3OH was obtained after careful design and synthesis. The structure of the [CuII 4GdIII 2] complex was adequately characterized by elemental analysis, FTIR, and UV–vis spectroscopy. The [CuII 4GdIII 2] complex crystallized in the monoclinic system, space group C2/c embraces four CuII ions with two coordination geometries: tetragonal pyramid and octahedron, two GdIII ions with nine coordinated tricapped trigonal prism geometry, two completely deprotonated octadentate (L)4– units, two coordinated methanol molecules, two bidentate bridging nitrate groups (μ 2-NO3 –), four bidentate chelating nitrate groups and two crystallized methanol molecules. The [CuII 4GdIII 2] complex ultimately constructs infinite 2D and 3D supramolecular structures via the intermolecular hydrogen bond interactions. Meanwhile, the fluorescence properties of the ligand (H4L) and its [CuII 4GdIII 2] complex were studied. The electronic structure and stability of the [CuII 4GdIII 2] complex were proved by density functional theory calculation.