Synthesis, crystal structures and spectroscopic properties of copper(I) complexes containing β-dialdiminato supporting ligands

Two mononuclear neutral copper(I) complexes, Cu(L¹)PPh₃ (1), Cu(L²)(PPh₃)₂ (2) ([L¹]⁻ = [{N(C₆H₃ⁱPr₂-2,6)C(H)}₂CPh]⁻; [L²]⁻ = [{N(C₆H₅)C(H)}₂CPh]⁻) have been synthesized and structurally characterized by X-ray crystallography. In complex 1, the copper(I) atom is in a distorted three-coordinate trigonal planar environment, whereas in complex 2 with the less sterically hindered β-dialdiminato ligand, the copper(I) atom is the centre of a four-coordinate distorted tetrahedron. At room temperature complexes 1 and 2 in a film of PMMA exhibit green emission at 543 and 549 nm with lifetimes of 5.28 and 5.32 ns, respectively.     

Oxime-functionalized diazamesocyclic derivates and their metal complexes: Effect of the ligand backbones and anions on the generation of novel monomeric and mono-μ-Cl dimeric Cu complexes

Two oxime-functionalized diazamesocyclic derivates, namely, N,N′-bis(acetophenoneoxime)-1,4-diazacycloheptane (H₂L¹) and N,N′-bis(acetophenonoxime)-1,5-diazacyclooctane (H₂L²), have been prepared and characterized. Both ligands (obtained in the hydrochloride form) can form stable metal complexes with Cu^II and Ni^II salts, the crystal structures of which were determined by X-ray diffraction technique. The reactions of H₂L¹ with Cu(ClO₄)₂ and Ni(ClO₄)₂ afford a penta-coordinated mononuclear complex [Cu(H₂L¹)Cl] · ClO₄ (1) and a four-coordinated monomeric [Ni(HL¹)] · ClO₄ (2), in which the ligand is monodeprotonated. The ligand H₂L² also forms a quite similar mononuclear [Ni(HL²)] · ClO₄ complex with Ni(ClO₄)₂, according to our previous work. However, reactions of different Cu^II salts [Cu(ClO₄)₂, CuCl₂ and Cu(NO₃)₂ for 3, and CuSO₄ for 4] with H₂L² in the presence of NaClO₄ yield two unusual mono-μ-Cl dinuclear Cu^II complexes [Cu₂(HL²)₂Cl] · (ClO₄) (3), and [Cu₂(H₂L²)(HL²)Cl] · (ClO₄)₂ · (H₂O)(4). These results indicate that the resultant Cu^II complexes (1, 3 and 4) are sensitive to the backbones of diazamesocycles and even auxiliary anions.     

Speciation, stability constants and structures of complexes of copper(II), nickel(II), silver(I) and mercury(II) with PAMAM dendrimer and related tetraamide ligands

The acid-base properties and Cu(II), Ni(II), Ag(I) and Hg(II) binding abilities of PAMAM dendrimer, L, and of the simple model compounds, the tetraamides of EDTA and PDTA, L¹, were studied in solution by pH-metric methods and by ¹H NMR and UV-Vis spectroscopy. PAMAM is hexabasic and six pK_a values have been determined and assigned. PAMAM forms five identifiable complexes with copper(II), [CuLH₄]⁶⁺, [CuLH₂]⁴⁺, [CuLH]³⁺, [CuL]²⁺ and [CuLH_-1]⁺ in the pH range 2-11 and three with nickel(II), [NiLH]³⁺, [NiL]²⁺ and [NiLH_-1]⁺ in the pH range 7-11. The complex [CuLH₄]⁶⁺, which contains two tertiary nitrogen and three amide oxygen atoms coordinated to the metal ion, is less stable than the analogous EDTA and PDTA tetraamide complexes [CuL¹]²⁺, which contain two tertiary nitrogen and four amide oxygen atoms, due to ring size and charge effects. With increasing pH, [CuLH₄]⁶⁺ undergoes deprotonation of two coordinated amide groups to give [CuLH₂]⁴⁺ with a concomitant change from O-amide to N-amidate coordination. Surprisingly and in contrast to the tetraamide complexes [CuL¹]²⁺, these two deprotonation steps could not be separated. As expected the nickel(II) complexes are less stable than their copper(II) analogues. The tetra-N-methylamides of EDTA, L¹(b), and PDTA form mononuclear and binuclear complexes with Hg(II). In the case of L¹(b) these have stoichiometries HgL¹(b)Cl₂, [HgL¹(b)H₋₂Cl₂]²⁻, [Hg₂L¹(b)Cl₂]²⁺, Hg₂L¹(b)H₋₂Cl₂ and [Hg₂L¹(b)H₋₅Cl₂]³⁻. Based on ¹H NMR and pH-metric data the proposed structure for HgL¹(b)Cl₂, the main tetraamide ligand containing species in the pH range <3-6.5, contains L¹(b) coordinated to the metal ion through the two tertiary nitrogens and two amide oxygens while the structure of [HgL¹(b)H₋₂Cl₂]²⁻, the main tetraamide ligand species at pH 7.5-9.0, contains the ligand similarly coordinated but through two amidate nitrogen atoms instead of amide oxygens. The proposed structure of [Hg₂L¹(b)Cl₂]²⁺, a minor species at pH 3-6.5, also based on ¹H NMR and pH-metric data, contains each Hg(II) coordinated to a tertiary amino nitrogen, two amide oxygens and a chloride ligand while that of [Hg₂L¹(b)H₋₅Cl₂]³⁻, contains each Hg(II) coordinated to a tertiary amino nitrogen, two amidate nitrogens, a chloride and a hydroxo ligand in the case of one of the Hg(II) ions. The parent EDTA and PDTA amides only form mononuclear complexes. PAMAM also forms dinuclear as well as mononuclear complexes with mercury(II) and silver(I). In the pH range 3-11 six complexes with Hg(II) i.e. [HgLH₄Cl₂]⁴⁺, [HgLH₃Cl₂]³⁺, [Hg₂LCl₂]²⁺, [Hg₂LH₋₁Cl₂]⁺, [HgLH₋₁Cl₂]⁻ and [HgLH₋₂Cl₂]²⁻ were identified and only two with Ag(I), [AgLH₃]⁴⁺ and [Ag₂L]²⁺. Based on stoichiometries, stability constant comparisons and ¹H NMR data, structures are proposed for these species. Hence [HgLH₄Cl₂]⁴⁺ is proposed to have a similar structure to [CuLH₄]⁶⁺ while [Hg₂LCl₂]²⁺has a similar structure to [Hg₂L¹(b)H₋₅Cl₂]³⁻.     

Synthesis, crystal structures and density functional theory study of dimeric copper(II) complexes of a tridentate Schiff-base ligand

Oxalate- or 4,4′-bipyridine-bridged dimeric copper(II) complexes, [Cu₂L₂(μ-ox)] (1) and [Cu₂L₂(μ-bipy)](BF₄)₂ (2) [where ox = oxalate, bipy = 4,4′-bipyridine, HL = N-(1H-pyrrol-2-ylmethylene)-2-pyridineethanamine, L⁻ = HL−H⁺], have been synthesised and characterised by elemental analysis, IR, UV-Vis and single crystal X-ray diffraction. Crystal structure determinations carried out on 1 and 2 reveal that 1 is an oxalate-bridged centrosymmetrical square pyramidal dimeric copper(II) complex while 2 is a 4,4′-bipyridine-bridged non-centrosymmetric square planar dinuclear copper(II) complex. Comparison of the optimised geometries with the corresponding crystal structures suggests that the B3LYP/LANL2DZ level can reproduce the structures of 1 and 2 on the whole. The electronic spectra of 1 and 2 predicted by B3LYP/LANL2DZ method show some blue shifts compared with their experimental data. Thermal analysis carried out on 1 shows that there is only one exothermal peak at about 260 °C and the residue is presumably Cu₂O₄N₆.     

Magnetic and catalytic properties of a new copper(II)-Schiff base 2D coordination polymer formed by connected helical chains

A dicyanamide bridged 2D polynuclear complex of copper(II) having molecular formula [Cu₂(L)(μ_1,5-dca)₂]_n (1) has been synthesized using the Schiff base ligand N,N′-bis(salicylidene)-1,3-diaminopentane, (H₂L) and sodium dicyanamide (dca). The complex presents a 2D hexagonal structure formed by 1,5-dca singly bridged helical chains connected through double 1,5-dca bridges. The chelating characteristics of the H₂L Schiff base ligand results in the formation of copper(II) dimer with a double phenoxo bridge presenting a very strong antiferromagnetic coupling in the copper(II) derivative (1) (J = −510 cm⁻¹). The dimeric asymmetric unit of 1 is very similar to the active site of the catechol oxidase and, as expected, also presents catalytic activity for the oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone in presence of O₂, as demonstrated by kinetic studies of this oxidation reaction monitored by absorption spectroscopy resulting in high turnover number (K_cat = 259 h⁻¹).     

Molecular interactions of zinc(II) cyclams with polycarboxylato ligands

Four new zinc(II) cyclams of the composition {Zn(L)(tp²⁻) · H₂O}_n (1), {Zn(L)(H₂bta²⁻) · 2H₂O}_n (2), [Zn₂(L)₂(ox²⁻)] 2ClO₄ · 2DMF (3), and Zn(L)(H₂btc⁻)₂ · 2DMF (4), where L = cyclam, tp²⁻ = 1,4-benzenedicarboxylate ion, H₂bta²⁻ = 1,2,4,5-benzenetetracarboxylate ion, ox²⁻ = oxalate ion, DMF = N,N-dimethylformamide, and H₂btc⁻ = 1,3,5-benzenetricarboxylate ion, have been synthesized and structurally characterized by a combination of analytical, spectroscopic and crystallographic methods. The carboxylato ligands in the complexes 1-4 show strong coordination tendencies toward zinc(II) cyclams with hydrogen bonding interactions between the pre-organized N-H groups of the macrocycle and oxygen atoms of the carboxylato ligands. The macrocycles in 1, 2, and 4 adopt trans-III configurations with the appropriate R,R,S,S arrangement of the four chiral nitrogen centers, respectively. However, the complex 3 shows an unusual cis V conformation with the R,R,R,R nitrogen configuration. The finding of strong interactions between the carboxylato ligands and the zinc(II) ions may provide additional knowledge for the improved design of receptor-targeted zinc(II) cyclams in anti-HIV agents.     

Structure, magnetic properties and nuclease activity of pyridine-2-carbaldehyde thiosemicarbazonecopper(II) complexes

New complexes of formulae [Cu(HL²)(H₂O)(NO₃)](NO₃) (1), [{Cu(L¹)(tfa)}₂] (2), [{Cu(L¹)}₂(pz)](ClO₄)₂ (3) and {[{Cu(L¹)}₂(dca)](ClO₄)}_n (4), where HL¹ = pyridine-2-carbaldehyde thiosemicarbazone, HL² = pyridine-2-carbaldehyde 4N-methylthiosemicarbazone, Htfa = trifluoroacetic acid (CF₃COOH), pz = pyrazine (C₄H₄N₂) and dca = dicyanamide [N(CN)₂]⁻, have been synthesized and characterized. The crystal structures of these compounds are built up of monomers (1), dinuclear entities with the metal centers bridged through the non-thiosemicarbazone coligand (2 and 3) and 1D chains of dimers (4). In all the cases, square-pyramidal copper(II) ions are present, except for the square-planar ones in 3. Magnetic measurements show antiferromagnetic couplings in 2, 3 and 4. The susceptibility data were fitted by the Bleaney-Bowers’ equation for copper(II) dimers derived from H = -2JS₁S₂ being the obtained J/k values −4.8, −4.3 and −5.1 K for compounds 2-4, respectively. The magnetic susceptibility of the already known [{Cu(HL¹)(tfa)}₂](tfa)₂ compound has been also measured for the first time. The J/k value is -0.3 K, lower than that in 2. The nuclease activity of 3 and 4 has been analyzed.     

Potential tridentate salicylaldehyde hydrazone of arylalkanoic acid coordinate to copper(II) acting as dinegative tetradentate ligands

A chiral Schiff base N-(S)-2-(6-methoxylnaphthyl)-propanoyl-N′-(2-hydroxylbenzylidene)hydrazine (H₂L) has been synthesized. Reaction of H₂L with Cu(OAc)₂ · H₂O led to the formation of a metal complex {[CuL] · H₂O · 2DMF}_∞ (1). In complex 1, the potential dinegative tridentate L²⁻ ligand acting as tetradentate bridging ligand coordinate to two metal ions so as to form a novel infinite metal-organic coordination chain structure. The enantiomerically pure ligand H₂L presents two different sets of signals in the ¹H NMR spectrum either in chloroform solution or in dimethylsulfoxide solution, showing the presence of both (E) and (Z) isomers. The X-ray structural investigations of H₂L revealed that it is the fully extended E-configuration in the solid state.     

Synthesis, structures and magnetic properties of 1D to 3D coordinated polymers based on series of flexible sulfide ligands

Five complexes [Mn₂O(L₁)₄]_n (1), [Co(L₂)(H₂O)₂]_n (2), [Co(L₃)₂(H₂O)₂]_n (3) and [Co(L₄)₂(4,4′-bpy)(H₂O)]_n (4) were obtained by using flexible organic ligands HL₁, HL₂, HL₃, and HL₄ in hydrothermal systems with cobalt, copper and manganese salts respectively (HL₁ = 2-(4-pyridylmethylthio)benzoic acid, HL₂ = 4-(4-pyridylmethylthio)benzoic acid, HL₃ = 2-(3-pyridylmethylthio)benzoic acid, HL₄ = 4-(2-pyridylmethylthio)benzoic acid). The five complexes have been characterized by X-ray single crystal diffraction, FT-IR spectrum and elemental analysis. Complex 1 is assembled to a 3D porous framework with Mn₂O units as nodes. Complex 2 shows 2D layer networks comprised of six-coordinated Co²⁺ centers and L₂⁻ anionic ions. Complexes 3 and 4 have different 1D double or single chain structures. Various non-covalent bonds such as hydrogen bonds, π?π interactions, H-bond grids and S?S weak interactions lead to interesting supramolecular frameworks. DC (direct current) temperature dependent magnetic susceptibilities suggest weak antiferromagnetic behaviors exist in 1, and single ion paramagnetic along with spin-orbit coupling behavior dominate in 3 and 4.     

Imidazole derivatives of binuclear copper (II) and nickel (II) complexes incorporating bis(1,4,7-triazacyclononan-1-yl) ligands

A series of new binuclear copper (II) and nickel (II) complexes of the macrocyclic ligands bis(1,4,7-triazacyclononan-1-yl)butane (L^but) and bis(1,4,7-triazacyclononan-1-yl)-m-xylene (L^mx) have been synthesized: [Cu₂L^butBr₄] (1), [Cu₂L^but(imidazole)₂Br₂](ClO₄)₂ (2), [Cu₂L^mx(μ-OH)(imidazole)₂](ClO₄)₃ (3), [Cu₂L^but(imidazole)₄](ClO₄)₄ · H₂O (4), [Cu₂L^mx(imidazole)₄](ClO₄)₄ (5), [Ni₂ L^but(H₂O)₆](ClO₄)₄ · 2H₂O (6), [Ni₂L^but(imidazole)₆](ClO₄)₄ · 2H₂O (7) and [Ni₂L^mx (imidazole)₄(H₂O)₂](ClO₄)₄ · 3H₂O (8). Complexes 1, 2, 7 and 8 have been characterized by single crystal X-ray studies. In each of the complexes, the two tridentate 1,4,7-triazacyclononane rings of the ligand facially coordinate to separate metal centres. The distorted square-pyramidal coordination sphere of the copper (II) centres is completed by bromide anions in the case of 1 and/or monodentate imidazole ligands in complexes 2, 4 and 5. Complex 3 has been formulated as a monohydroxo-bridged complex featuring two terminal imidazole ligands. Complexes 6-8 feature distorted octahedral nickel (II) centres with water and/or monodentate imidazole ligands occupying the remaining coordination sites. Within the crystal structures, the ligands adopt trans conformations, with the two metal binding compartments widely separated, perhaps as a consequence of electrostatic repulsion between the cationic metal centres. The imidazole-bearing complexes may be viewed as simple models for the coordinative interaction of the binuclear complexes of bis (tacn) ligands with protein molecules bearing multiple surface-exposed histidine residues.     

Palladium(II) complexes obtained from 3,4-bis(cyanamido)cyclobutane-1,2-dione dianion

Three palladium(II) complexes have been synthesized, using 3,4-bis(cyanamido) cyclobutane-1,2-dione dianion (3,4-bis(cyanamido)squarate or 3,4-NCNsq²⁻): [Pd(en)(3,4-NCNsq)] · 1.5H₂O (1) (en=1,2-diaminoethane), [Pd(en)(3,4-(NC(O)NH₂)sq)] · 0.5H₂O (2) and K₃Na[Pd₂(3,4-(NCN)₂sq)₄] · 5H₂O (3). Complex 1 has been characterized by elemental analysis, IR and ¹³C NMR spectroscopies. Complexes 2 and 3 have been characterized by single-crystal X-ray diffraction. In complex 2, the unusual hydration of the cyanamido ligand was observed, it proceeds in the coordination sphere of the palladium and leads to a chelating urea squarate ligand. Complex 3 is an anionic dinuclear complex containing four bridging cyanamido squarate ligands. In complexes 2 and 3, the 3,4-NCNsq²⁻ ligand (hydrated or not) is, for the first time, coordinated to the metal atom by the two amido nitrogen atoms, either in a chelating mode (complex 2) or in a bridging mode giving a short Pd ? Pd distance of 2.8866(15) Å (complex 3). Electrochemical studies in acetonitrile and dmf solutions have been performed on complexes 1 and 3.     

Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction

Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh₃)₂(CO)(NC₄H₃C(O)CH₃)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (ΔH^‡ = 195 ± 41 kJ mol⁻¹; ΔS^‡ = 232 ± 62 J mol⁻¹ K⁻¹); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2′-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.     

Rhenium(III) and technetium(III) complexes with 2-mercapto-1,3-azole ligands and X-ray crystal structures

Reactions of labile [MCl₃(PPh₃)₂(NCMe)] (M = Tc, Re) precursors with 1H-benzoimidazole-2-thiol (H₂L¹), 5-methyl-1H-benzoimidazole-2-thiol (H₂L²) and 1H-imidazole-2-thiol (H₂L³), in the presence of PPh₃ and [AsPh₄]Cl gave a new series of trigonal bipyramidal M(III) complexes [AsPh₄]{[M(PPh₃)Cl(H₂L^1-3)₃]Cl₃} (M = Re, 1-3; M = Tc, 4-6). The molecular structures of 1 and 3 were determined by X-ray diffraction. When the reactions were carried out with benzothiazole-2-thiol (HL⁴) and benzoxazole-2-thiol (HL⁵), neutral paramagnetic monosubstituted M(III) complexes [M(PPh₃)₂Cl₂(L^4,5)] (M = Re, 8, 9; M = Tc, 10, 11) were obtained. In these compounds, the central metal ions adopt an octahedral coordination geometry as authenticated by single crystal X-ray diffraction analysis of 8 and 11. Rhenium and technetium complexes 1, 4 and rhenium chelate compounds 8, 9 have been also synthesized by reduction of [MO₄]⁻ with PPh₃ and HCl in the presence of the appropriate ligand. All the complexes were characterized by elemental analyses, FTIR and NMR spectroscopy.     

Synthesis, structures and luminescent properties of novel coordination polymers constructed by lanthanide salts and benzimidazole-5,6-dicarboxylic acid

Two three-dimensional (3D) novel lanthanide complexes with the H₂Lbenzimidazole-5,6-dicarboxylate [Ln₂L₃(H₂O)] [Ln = Eu (1), Tb (2)] and one two-dimensional (2D) novel lanthanide complex [Pr(L)(HL)H₂O]·H₂O (3) were synthesized by hydrothermal reaction at 180 °C and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The result showed that complexes 1 and 2 are isostructural and build porous 3D networks by L²⁻ groups linking Ln(III) atoms via tetradentate (bridging and bridging) and pentadentate (bridging/chelating and bridging) coordination modes. Complex 3 is a eight-coordinated Pr(III) chain complex, exhibiting a 2D polymeric network with parallel Pr-carboxylate chains along the crystallographic c-axis. In addition, it is found that in these structures, coordination modes of L²⁻ and HL⁻ are versatile and can adopt different conformations according to distinct dimensions of polymeric structures. The photoluminescent properties of 1, 2 and thermogravimetric analyses of the three complexes were discussed in detail.     

Coordination chemistry of heterocycle-functionalized diazamesocycles: tuning the productive Ni complexes through altering the pendants of ligands

In order to further understand the coordination chemistry of diazamesocyclic systems, a series of mononuclear Ni^II complexes with 1,4-diazacycloheptane (DACH) functionalized by additional imidazole or pyridine donor pendants, including [NiL¹](ClO₄)₂ · H₂O (1), [NiL¹Cl](ClO₄) (2), [NiL²Cl](ClO₄) · CH₃OH (3), [NiL²Cl][NiL²](ClO₄)₃ (4) and [NiL³](ClO₄)₂ (5), where L¹ = 1,4-bis(N-1-methylimidazol-2-yl-methyl)-1,4-diazacycloheptane, L² = 1,4-bis(pyridyl-2-yl-methyl)-1,4-diazacycloheptane, and L³ = 1,4-bis-(imidazol-4-yl-methyl)-1,4-diazacycloheptane, have been prepared and characterized. A detailed study on the solid structures and solution spectra of these complexes indicates that tetradentate ligands L¹, L² and L³ would lead to new Ni^II complexes with different coordination environments in the solid states and solution. The N-methyl substituted imidazole functionalized ligand L¹ forms green compound 2 and yellow product 1; while the pyridine functionalized ligand L² affords red product 4 and green complex 3; the ligand L³ results in only one stable mononuclear Ni^II product 5. The solution behaviors of these interesting compounds were also investigated by UV-Vis technique.     

Lanthanide(III) complexes with phosphoryl containing 1,8-naphthyridine: Crystal structures and vibrational spectra

The complexes of 2-[2-(diphenylphosphoryl)prop-2-yl]-1,8-naphthyridine (L) with lanthanide nitrates Ln(NO₃)₃ (Ln = Nd, Eu, Lu) were investigated to elucidate the coordination ability of a novel type of potentially tridentate ligands - phosphorylalkyl substituted naphthyridines. The X-ray crystal structures of [NdL₃]³⁺ · 3(NO₃)⁻ · MeCN (1), [EuL₃]³⁺ · 3(NO₃)⁻ · [Eu(NO₃)₃ · 4H₂O] · MeCN (2), and [LuL₃]³⁺ · 3(NO₃)⁻ · [Lu(NO₃)₃ · 3H₂O] · 2 MeCN · 0.5 H₂O (3) are reported together with their IR and Raman spectra. All the compounds studied contain isostructural [LnL₃]³⁺ cations and three NO₃⁻ counterions. Coordination of each L appears to be O,N,N tridentate-cyclic and coordination number of Ln is nine. Vibrational spectra of 1-3 are also compared with that of free ligand and model compounds.     

N,N′-Bis(3-methoxysalicylidene)propane-1,2-diamine mononuclear 4f and heterodinuclear Cu-4f complexes: Synthesis, crystal structure and electrochemical properties

Reactions of H₂L [H₂L = N,N′-bis(3-methoxysalicylidene)propane-1,2-diamine] and Ln(NO₃)₃ · 6H₂O give rise to two different mononuclear 4f complexes, namely, {[(H₂L)La(NO₃)₃(MeOH)] · H₂O}_n (1) and [(H₂L)Nd(NO₃)₃] (2). Further additions of Cu(Ac)₂ · H₂O to the mononuclear 4f complexes yield expected heterodinuclear Cu-4f complexes [LCu(Me₂CO)Ln(NO₃)₃] (3, Ln = Nd; 4, Ln = Eu; 5, Ln = Dy). Complex 1 is a unique 1D polymeric chain structure, and 2 is one of the few structurally characterized discrete hexadentate salen-type mononuclear 4f complexes. Complexes 3-5 are similar to their analogues. However, they are prepared by a reversed synthetic route in contrast to their isomorphic complexes. Electrochemical behavior of heterodinuclear Cu-4f complexes 3-5 has been examined by cyclic voltammetry in acetonitrile. The redox potential of heterodinuclear Cu-4f complexes 3-5 shows significant anodic shift comparing to that of mononuclear copper complex (LCu). A tendency of anodic shift was observed in a sequence of 3 < 4 < 5. This results from the modulating effect of coordination geometry around Cu(II) ion on redox potential.     

Metal-regulated assemblies of Cu, Ni, and Zn complexes with isoquinoline-3-carboxylate displaying diverse supramolecular networks

Three distinct coordination complexes, viz. {[Cu(μ-L)₂] · (H₂O)₄}_n (1), [Ni(L)₂(CH₃OH)₂] (2), and [Zn(L)₂(H₂O)₂] · (H₂O)₂ (3), have been prepared by the reactions of metal nitrates with isoquinoline-3-carboxylic acid (HL). X-ray single-crystal diffraction suggests that 1 is a 1D chain coordination polymer in which the Cu^II ions are connected by carboxylates, whereas complexes 2 and 3 represent discrete mononuclear species. In all the cases, the coordination entities are further organized via hydrogen-bonding interactions to generate multifarious supramolecular networks. Remarkably, a well-resolved 1D water morphology is observed for the first time in the crystalline lattice of 1 along [1 0 0], which consists of edge-sharing tetrameric subunits and stabilized by the metal-organic host surroundings.     

Effect of anionic co-ligands on structure and magnetic coupling of bis(μ-phenoxo)-bridged dinuclear copper(II) complexes

Two phenoxo bridged dinuclear Cu(II) complexes, [Cu₂L₂(NO₂)₂] (1) and [Cu₂L₂(NO₃)₂] (2) have been synthesized using the tridentate reduced Schiff-base ligand 2-[(2-dimethylamino-ethylamino)-methyl]-phenol (HL). The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. The structures of the two compounds are very similar having the same tridentate chelating ligand (L) and mono-dentate anionic ligand nitrite for 1 and nitrate for 2. In both complexes Cu(II) is penta-coordinated but the square pyramidal geometry of the copper ions is severely distorted (Addison parameter (τ) = 0.33) in 1 while the distortion is quite small (average τ = 0.11) in 2. These differences have marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = −140.8 and −614.7 cm⁻¹ for 1 and 2, respectively) show that the coupling is much stronger in 2.     

Copper(II) complexes with monocarboxylate ligands bearing different substituent groups: Synthesis and spectroscopic studies

In our continuing efforts to explore the effects of substituent groups of ligands in the formation of supramolecular coordination structures, seven new Cu^II complexes formulated as [Cu₂(L¹)₄(DMF)₂] (1), {[Cu₂(L¹)₄(Hmta)](H₂O)_0.75}_∞ (2), [Cu₂(L²)₄(2,2′-bipy)₂] (3), [Cu₂(L³)₄(H₂O)₂] (4), [Cu₂(L³)₄(Hmta)]_∞ (5), [Cu₂(L³)₄(Dabco)]_∞ (6) and [Cu₂(L³)₄(Pz)]_∞ (7) with three monocarboxylate ligands bearing different substituent groups HL¹-HL³ (HL¹ = phenanthrene-9-carboxylic acid, HL² = 2-phenylquinoline-4-carboxylic acid, HL³ = adamantane-1-carboxylic acid, Hmta = hexamethylenetetramine, 2,2′-bipy = 2,2′-bipyridine, Dabco = 1,4-diazabicyclo[2.2.2] octane and Pz = pyrazine), have been prepared and characterized by X-ray diffraction. In 1, 2 and 4-7, each Cu^II ion is octahedrally coordinated, and carboxylate acid acts as a syn-syn bridging bidentate ligand. While each Cu^II ion in 3 is penta-coordinated in a distorted square-pyramidal geometry. 1 and 4 both show a dinuclear paddle-wheel block, while 2, 5, 6 and 7 all exhibit an alternated 1D chain structure between dinuclear paddle-wheel units of the tetracarboxylate type Cu₂-(RCO₂)₄ and the bridging auxiliary ligands Hmta, Dabco and Pz. Furthermore, 3 has a carboxylic unidentate and μ_1,1-oxo bridging dinuclear structure with the chelating auxiliary ligand 2,2′-bipy. Moreover, complexes 1-6 were characterized by electron paramagnetic resonance (EPR) spectroscopy.