The key role of hydrogen bonding in the nuclearity of three copper(II) complexes with hydrazone-derived ligands and nitrogen donor heterocycles

Three new Cu(II) complexes of formula [Cu(L¹)(pyz)(CH₃OH)]ClO₄ (1), [Cu(L¹)(4,4′-bpy)(ClO₄)]·0.5H₂O (2) and [{Cu(L²)(ClO₄)}₂(μ-4,4′-bpy)] (3) have been synthesised by using pyrazine (pyz) and 4,4′-bipyridine (4,4′-bpy) and tridentate O,N,O-donor hydrazone ligands, L¹H and L²H, obtained by the condensation of 1,1,1-trifluoro-2,4-pentanedione with salicyloylhydrazide and benzhydrazide, respectively. The ligands and their complexes have been characterized by elemental analyses, FT-IR, and UV-Vis spectroscopies. Single crystal X-ray structure analysis evidences the metal ion in a slightly deformed square pyramidal geometry in all the complexes. However complexes 1 and 2 are mononuclear with pyz and 4,4′-bpy, respectively, showing an unusual monodentate behavior, while complex 3 is dinuclear with 4,4′-bpy adopting the typical bridging coordination mode. Self assembly of the complex units by hydrogen bonding interactions produces one-dimensional arrangement in each crystal packing. The magnetic characterization of complex 3 indicates a weak antiferromagnetic exchange interaction between the Cu(II) ions (J = −0.96 cm⁻¹) mediated through the long 4,4′-bpy bridge. Electrochemical behavior of the complexes is also discussed.     

Phosphodiester hydrolysis and specific DNA binding and cleavage promoted by guanidinium-functionalized zinc complexes

Two new Zn(II) complexes containing guanidinium groups, [Zn(L¹)Cl₂](ClO₄)₂ · H₂O · CH₃OH (1) and [Zn(L²)Cl₂](ClO₄)₂ · 0.5H₂O (2), were synthesized and characterized (L¹ = 5,5′-di[1-(guanidyl)methyl]-2,2′-bipyridyl bication and L² = 6,6′-di[1-(guanidyl)methyl]-2,2′-bipyridyl bication). Both complexes are able to catalyze bis(p-nitrophenyl) phosphate (BNPP) hydrolysis efficiently. Obtained kinetic data reveal that both 1 and 2 show nearly 300- and 600-fold rate enhancement of BNPP hydrolysis, respectively, compared to their simple analogue without the guanidinium groups [Zn(bpy)Cl₂] (bpy = 2,2′-bipyridy) (3). Enhanced acceleration for cleavage of BNPP could be attributed to cooperative interaction between the Zn(II) ion and the guanidinium groups by electrostatic interaction and H-bonding. Studies on inhibition of sequence-specific endonucleases (DraI and SmaI) by complexes show that 1 and 2 are able to recognize nucleotide sequence, -TTT^AAA-, and highly effectively cleave the plasmid DNA in the presence of hydrogen peroxide, while 3 has no specific binding to the DNA target sequences and only shows low DNA cleavage activity.     

Bis(O2S2 macrocycle) complexes of palladium(II)

Two isomeric dibenzo-O₂S₂ macrocycles L¹ and L² have been synthesised and their coordination chemistry towards palladium(II) has been investigated. Two-step approaches via reactions of 1:1-type complexes, [cis-Cl₂LPd] (1a: L = L¹, 1b: L = L²), with different O₂S₂ macrocycle systems (L¹ and L²) have led to the isolation of the following bis(O₂S₂ macrocycle) palladium(II) complexes in the solid state: [Pd(L¹)₂](ClO₄)₂ (2a) and a mixture of [Pd(L¹)₂](ClO₄)₂ (2a) + [Pd(L²)₂](ClO₄)₂ (2b).     

Four new copper(II) complexes with 1,3-tpbd ligand: Synthesis, crystal structures, magnetism, oxidative and hydrolytic cleavage of pBR322 DNA

Four copper(II) complexes [Cu₂(1,3-tpbd)Cl₄]·EtOH (1), {[Cu₂(1,3-tpbd)(μ-Cl)₂](ClO₄)₂(H₂O)_4.5 (NaClO₄)}_∞ (2), [Cu₂(1,3-tpbd)(1,10-phen)₂(H₂O)₂](ClO₄)₄ (3) and [Cu₂(1,3-tpbd)(2,2′-bpy)₂(H₂O)₂](ClO₄)₄ (4) (1,3-tpbd = N,N,N′,N′-tetrakis(2-pyridylmethyl)benzene-1,3-diamine) have been synthesized and characterized by X-ray single crystal structure analysis. Variable-temperature magnetic susceptibility studies (2-300 K) indicate the existence of antiferromagnetic coupling between the copper(II) ions in complexes 2 and 3. The interactions of the four complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescent spectroscopy, circular dichroism spectroscopy, viscosity and cyclic voltammetry, and the modes of CT-DNA binding to the complexes have been proposed. Furthermore, DNA cleavage activities by the four complexes were performed in the presence and absence of external agents, the results indicate that their cleavage activities have been promoted in the presence of external agents. Mechanism investigation shows that the four complexes could cleave DNA through both oxidative and hydrolytic processes. In the four copper(II) complexes, complex 2 showed highest cleavage activity with the pseudo-Michaelis-Menten kinetic paraments k_cat = 5.16 h⁻¹ and K_m = 3.6 × 10⁻⁵ M.     

Structure and spectroelectrochemical property of a ruthenium complex containing phenanthroline-quinone, and assembly of the complexes on a gold electrode

Ruthenium complexes containing pdon (pdon = 1,10-phenanthroline-5,6-dione) were synthesized. Their spectroscopic and electrochemical properties were examined. The molecular structure with [Ru(pdon)(bpy)₂](ClO₄)₂ ([1](ClO₄)₂) (bpy = 2,2′-bipyridyl) was determined by single crystal X-ray diffraction. The optically transparent thin-layer electrochemical measurements confirm that the quinone form of [1](ClO₄)₂ is reduced to the semi-quinone state in acetonitrile (E°′ = −8 mV). Comparing the model complex, [1](ClO₄)₂, and metal-free pdon, the positive charge on two carbon atoms of the o-quinone group is bigger than that of metal-free pdon. The assemblies of the complexes were finally examined using ligand substitution.     

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.     

Extended molecular networks based on Zn and Cd imparting N-substituted imidazole

Synthesis of complexes with the formulations [M(CPI)₂Cl₂] (M = Zn, 1; M = Cd, 4) and [M(CPI)₆](X)₂ (M = Zn, X = NO₃⁻, 2; X = ClO₄⁻, 3; M = Cd, X = NO₃⁻, 5; X = ClO₄⁻, 6) have been achieved from the reactions of MCl₂, M(NO₃)₂·xH₂O and M(ClO₄)₂·xH₂O (M = Zn, Cd) with 1-(4-cyanophenyl)-imidazole (CPI). Complexes 1-6 have been characterized by elemental analyses and spectral studies (IR, ¹H, ¹³C NMR, electronic absorption and emission). Molecular structures of 1, 2, 3 and 6 have been determined crystallographically. Weak interaction studies on the complexes revealed presence of various interesting motifs resulting from C-H···N, C-H···Cl and π-π stacking interactions. The complexes under study exhibit strong luminescence at ∼450 nm in DMSO at room temperature.     

Hydrolytic cleavage of double-strand DNA by the water-soluble dicobalt(III) complexes of 1,4,7-Triazacyclononane-N-acetate

Three water-soluble dicobalt(III) complexes, [Co₂L₂(µ-OH)₂](ClO₄)₂·5H₂O (1), [Co₂L₂(µ-OH)₂](ClO₄)₂·CH₃OH·H₂O(2); [Co₂L₂(µ-OH)₂](ClO₄)₂·4H₂O(3) (L = 1,4,7-triazacyclononane-N-acetate monoanion), were prepared to serve as nuclease mimics. The complexes were characterized by X-ray, IR and UV-vis spectroscopy as well as ESI-MS. Three complexes exhibit similar structures, just with different solvent molecules. The electrospray mass spectrum of 1 in solution indicates that dinuclear ion [Co₂L₂(µ-OH)₂-H⁺] ⁺ (4) is the active species. In the absence of any reducing agent, the complexes cleave plasmid pBR322 DNA was performed and its hydrolytic mechanism was demonstrated with radical scavengers, anaerobic reaction and T4 ligase. The kinetic aspects of DNA cleavage under pseudo- or true-Michaelis-Menten conditions are also detailed, kinetic parameters (k_cat, K_M) were calculated to be 3.57 h^− 1, 6.92 × 10^− 4 M; 0.28 h^− 1, 1.9 × 10^− 5 M for 4, respectively.     

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.     

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.     

Anion effects on construction of Zn compounds with a chelating ligand bis(2-pyridylmethyl)amine and their catalytic activities

Three Zn^II complexes containing bispicam ligands (bispicam = bis(2-pyridylmethyl)amine), [Zn(bispicam)₂](NO₃)₂·2CH₃OH 4A, [Zn(bispicam)(NO₃)₂] 4B, and [Zn(bispicam)₂](OTf)₂6, were obtained, and their structures were determined by X-ray crystallography. Complexes of the general formulation [Zn(bispicam)₂]X₂ (X = Cl⁻ (1), Br⁻ (2), I⁻ (3), NO₃⁻ (4A), ClO₄⁻ (5), and OTf⁻ (6)) show fac geometric isomers (a) or enantiomers (c) and (d) according to anions. Moreover, complexes 4-6 could carry out the catalytic transesterification of a range of esters with methanol under the mild conditions. Importantly, the catalyst 4B with an unsaturated structure has shown better efficiency than the catalysts, 4A, 5, and 6, having saturated structures. To explain this reactivity difference, two different reaction mechanisms have been proposed (metal-based vs. amide N-H-based).     

Synthesis, spectral characterization, and single crystal X-ray structures of a series of manganese-2,2′-bipyridine complexes derived from substituted aromatic carboxylic acids

Reaction of [Mn(2,2′-bpy)₂(OAc)](ClO₄)(H₂O) with a series of aromatic carboxylic acids yields new Mn(II)carboxylates [Mn(2,2′-bpy)₂(L)](ClO₄)}₂ (1-3), [Mn(2,2′-bpy)₂(L)₂] (4-5) and [Mn(2,2′-bpy)₂(L)(H₂O)](ClO₄) (6) (L = 2-aminobenzoate (2-aba) (1), 4-hydroxybenzoate (4-hba) (2), thiophene-2-carboxylate (2-tca) (3), 2-hydroxynapthoate (2-hnapa) (4), 3,5-diisopropylsalicylic acid (dipsa) (5), 2,4,6-triisopropylbenzoate (tipba) (6)). The new compounds have been characterized with the aid of elemental analysis, spectroscopy, and single-crystal X-ray diffraction studies. Compounds 1-3, which have been synthesized from less bulky carboxylic acids, are dimeric in the solid-state. Compounds 4-6, which are derived from more bulkier aromaric carboxylic acids, exist as monomeric complexes. In the case of 6, where very bulky 2,4,6-triisopropyl benzoic acid is used as the starting material, only one carboxylate ligand binds to the metal, resulting in a cationic complex. Interestingly in all the six complexes, the C-H hydrogen atoms of the 2,2′-bpy ligands are involved in extensive hydrogen bonding with the carboxylate oxygen atoms of the adjacent molecules and hence form non-covalent 1-D or 2-D aggregates in the solid state.     

Synthesis, structures and magnetic properties of nickel(II), manganic(II) and zinc(II) complexes containing pyridyl-substituted nitronyl nitroxide and tris(2-benzimidazolymethyl)amine

Three new magnetic compounds were synthesized by using 2-(2′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (NIT2Py) and tris(2-benzimidazolymethyl)amine (NTB) as ligands. The structures and magnetic properties of the complexes with formula [Ni(NIT2Py)(NTB)](ClO₄)₂(CH₃OH) 1, [Mn(NIT2Py)(NTB)](ClO₄)₂2 and {[Zn(NIT2Py)₂(CH₃OH)₂](ClO₄)₂}{[Zn(NTB)(H₂O)](ClO₄)₂} 3 were characterized. Compounds 1 and 2 both have [M(NIT2Py)(NTB)] structural units, where the metal ion is in an octahedral environment bound to one NIT2Py through one pyridyl nitrogen atom and one nitroxide oxygen atom. However, compound 3, the chelating zinc ion has two crystallographically independent molecules in the asymmetric unit: one is six coordinated octahedral structure [Zn(NIT2Py)₂(CH₃OH)₂](ClO₄)₂, and the other one is five coordinated pyramidal structure [Zn(NTB)(H₂O)](ClO₄)₂. The magnetic behaviors of these compounds indicate that both the nickel ion and the manganese ion are antiferromagnetically coupled with the NIT2Py ligand with a coupling constant of −19.44 and −0.37 cm⁻¹, respectively, whereas two NIT2Py ligands in compound 3 are ferromagnetically coupled with a coupling constant of 19.1 cm⁻¹.     

Interaction of free functional group with platinum(II) center in cyclometalated complexes: A structural and photophysical property investigation

A series of flexible multidentate ligands containing N,P-donor, 2-[N-(diphenylphosphino)methyl]amino-pyridine (L¹), 2-[N-bi-(diphenylphosphino) methyl]amino-pyridine (L²), 2-[N-(diphenylphosphino)methyl]amino-7-methyl-1,8-naphthyridine (L³) and 4-[(N-diphenylphosphino)methyl]amino-pyridine) (L⁴) have been synthesized. The mono- and dinuclear cyclometalated platinum(II) complexes [Pt(C^N^N)L¹]ClO₄ (HC^N^N = 6-phenyl-2,2′-bipyridine), [Pt₂(C^N^N)₂L¹](ClO₄)₂, [Pt₂(C^N^N)₂L²](ClO₄)₂, [Pt(C^N^N)L³]ClO₄ and [Pt₂(C^N^N)₂L⁴](ClO₄)₂ were prepared and their structures determined by X-ray crystal analysis. These complexes exhibit long-lived bright orange emissions ranging from 560 to 610 nm in the solid state at room temperature. In solution, dinuclear complexes have emissions with higher quantum yields than mononuclear complexes. This can be attributed to intramolecular interaction of free functional group with Pt(II) at axial position, resulting in the quenching of phosphorescence for platinum(II) complexes in the ³MLCT excited state.     

Syntheses, crystal structures and magnetic properties of trinuclear and [3 × 1 + 1 × 2] pentanuclear complexes derived from a compartmental ligand: Role of solvent on nuclearity and number of components

Reaction of [Cu^IIL⊂(H₂O)] (H₂L = N,N′-ethylenebis(3-ethoxysalicylaldimine)) with nickel(II) perchlorate in 1:1 ratio in acetone produces the trinuclear compound [(Cu^IIL)₂Ni^II(H₂O)₂](ClO₄)₂ (1). On the other hand, on changing the solvent from acetone to methanol, reaction of the same reactants in same ratio produces the pentametallic compound [(Cu^IIL)₂Ni^II(H₂O)₂](ClO₄)₂·2[Cu^IIL⊂(H₂O)]·2MeOH (2A), which loses solvated methanol molecules immediately after its isolation to form [(Cu^IIL)₂Ni^II(H₂O)₂](ClO₄)₂·2[Cu^IIL⊂(H₂O)] (2B). Clearly, formation of 1 versus 2A and 2B is solvent dependent. Crystal structures of 1 and 2A have been determined. Interestingly, compound 2A is a [3 × 1 + 1 × 2] cocrystal. The cryomagnetic profiles of 1 and 2B indicate that the two pairs of copper(II)···nickel(II) ions in the trinuclear cores in both the complexes are coupled by almost identical moderate antiferromagnetic interaction (J = −22.8 cm⁻¹ for 1 and −26.0 cm⁻¹ for 2B).     

Ruthenium polypyridyl complexes containing the bischelating ligand 2,2′-azobispyridine. Synthesis, characterization and crystal structures

Three ruthenium polypyridyl compounds of structural formula [Ru(apy)(tpy)Lⁿ⁻](ClO₄)_(2−n) (apy = 2,2′-azobispyridine; tpy = 2,2′:6′,2″-terpyridine; L = Cl, H₂O, CH₃CN) (1a-c) were synthesized and crystallized. These complexes were fully characterized by means of 1D and 2D ¹H NMR spectroscopy, as well as mass spectrometry and elemental analysis. Although in theory two isomers are possible, i.e. the one in which the central N atom in tpy is trans to the azo N in apy and the one in which the former is trans to the pyridine N in apy, in all cases only the latter was observed. The molecular structures of the compounds were elucidated by single-crystal X-ray diffraction.     

Zinc(II) complexes with 1,8-naphthyridine-based ligand: Crystal structures and luminescent properties

The reactions of 2,4-dimethyl-7-(2-pyridylamino)-1,8-naphthyridine (L1) with Zn(ClO₄)₂ · 6H₂O, and bis(5,7-dimethyl-1,8-naphthyrid-2-yl)amine ligand (L2) with Zn(OAc)₂ · 2H₂O, ZnCl₂ or Zn(ClO₄)₂ · 6H₂O afforded four blue luminescent zinc(II) complexes, [Zn(L1)₂](ClO₄)₂ · 2CH₂Cl₂ (1), [Zn(L2)(OAc)₂] · CH₂Cl₂ (2), [Zn(L2)₂][ZnCl₄] · 3.5CH₂Cl₂ (3) and [Zn(L2)₂](ClO₄)₂ (4), respectively. Crystal structures of complexes 1-3 have been determined by X-ray structural analyses as mononuclear complexes with pseudo-tetrahedral geometry. The crystal packing of 1 reveals the coordination cation which is self-assembled to stair chains through aromatic π-π interactions. The intermolecular N-H?O hydrogen bond in 2 generates a centrosymmetric H-bonded dimer. However, the crystal lattice of 3 shows that the molecules are linked by extensive intermolecular hydrogen bonds between the amino groups and the anions, resulting in a one-dimensional zigzag chain. Furthermore, these molecular pairs or chains were self-assembled to two-dimensional sheets or three-dimensional networks through aromatic π-π interactions. All the zinc(II) complexes display intense intraligand ¹(π-π^∗) fluorescence with λ_max at 380 and 393 nm for 1, 385 and 404 nm for 2-4 in methanol at room temperature, respectively. Emission quantum yields of these complexes are in the range from 0.41 to 0.57. The broad emission bands in their solid-state emission spectra are attributed to intraligand ¹(π-π^∗) transition and aromatic π-π interactions as well.     

An oxamato bridged trinuclear copper(II) complex: Synthesis, crystal structure, reactivity, DNA binding study and magnetic properties

A linear tri-nuclear oxamato bridged copper(II) complex [Cu₃(pba)(dpa)₂(H₂O)(ClO₄)](ClO₄)·H₂O (1) (pbaH₄ = 1,3-propanediylbis(oxamic acid), dpa = 2,2′-dipyridylamine) was isolated from the reaction mixture of Na₂[Cu(pba)]·3H₂O, copper perchlorate hexahydrate and dipyridylamine in methanol. On reaction with dpa or DMF in basic medium (KOH) at ambient temperature complex 1 changed to dinuclear oxalate bridged copper(II) derivatives, [Cu₂(μ-C₂O₄)(dpa)₄](ClO₄)₂ (2) and [Cu₂(μ-C₂O₄)(dpa)₂(DMF)₂](ClO₄)₂ (3), respectively. The complexes 1, 2 and 3 have been characterized by physicochemical and spectroscopic tools, and also by the X-ray single crystal analysis. The hydrolysis of 1 in basic medium and thermo-gravimetric analysis has been studied. Absorption and emission spectral studies showed that complex 1 interacts with calf thymus-DNA (CT-DNA) with a binding constant (K_b) of 4.01 × 10⁴ M⁻¹ and linear Stern-Volmer quenching constant (K_sv) of 6.9 × 10⁴. A strong anti-ferromagnetic interaction with a coupling constant J_CuCu of 320.0 ± 0.3 cm⁻¹ was observed from the study of magnetic behavior of complex 1 in the temperature range of 2-300 K. Electrochemical equivalency of three copper(II) ions in 1 was identified by getting only one quasi reversible cyclic voltammogram.     

Synthesis and characterization of imidazolate-bridged polynuclear copper complexes

Copper(II) complexes of N4-donor ligands containing imidazole moieties, 4-[bis(1-methylimidazole-2-yl-methyl)aminomethyl]imidazole (Him-im₂) and 4-[bis(1-methylimidazole-2-yl-methyl)aminoethyl]imidazole (Hhis-im₂), were prepared, and [Cu(Him-im₂)Cl]ClO₄ (1) and [Cu(Hhis-im₂)Cl]ClO₄ (2) were structurally characterized by the X-ray diffraction method. Complexes 1 and 2 have a mononuclear structure with a coordinated chloride ion. The geometry of the Cu(II) center in 1 was found to be 5-coordinate trigonal-bipyramidal, whereas that of 2 was square-pyramidal. Complexes 1 and 2 showed different absorption and EPR spectra in MeOH, indicating that these compounds in solution maintain the structures revealed in the solid state. On the other hand, the reaction of Him-im₂ with Cu(ClO₄)₂ · 6H₂O under basic conditions gave a tetranuclear Cu(II) complex, [Cu₄(im-im₂)₄](ClO₄)₄ (3), whereas using the ligand Hhis-im₂ gave two kinds of polynuclear complexes [Cu₄(his-im₂)₄](ClO₄)₄ (4) and [Cu₆(his-im₂)₆](ClO₄)₆ (5) exhibiting discretely different structures. X-ray crystal structure analysis of the polynuclear complexes revealed their cyclic structures bridged by the imidazolate moiety. The geometry difference of the Cu(II) centers between 1 and 2 is thus concluded to determine the structures of tetranuclear complexes 3 and 4, respectively. Temperature dependent magnetic susceptibility measurements of complexes 3, 4, and 5 have shown an antiferromagnetic exchange interaction with a coupling constant of J = −32.5, −27.1 and −22.8 cm⁻¹, respectively.     

Diastereoisomerically pure pyrazole-3,5-dicarboxylate-bridged dinuclear ruthenium(II) and osmium(II) complexes of 2,2-bipyridine: structural, electrochemical and spectral studies

Pyrazole-3,5-dicarboxylate-bridged dinuclear ruthenium(II) and osmium(II) complexes of 2,2^′-bipyridine of composition [(bpy)₂Ru(pzdc)Ru(bpy)₂](ClO₄) · H₂O (1) and [(bpy)₂Os(pzdc)Os(bpy)₂](ClO₄) · H₂O (2) have been obtained in high yield and have been separated to their homochiral (ΛΛ/ΔΔ) rac (1a, 2a) and heterochiral (ΛΔ/ΔΛ) meso (1b, 2b) diastereoisomers. The distinctive structural features of these diastereoisomers have been characterized by 1-D and 2-D ¹H NMR spectroscopy. The X-ray crystal structure of rac-[(bpy)₂Os(pzdc)Os(bpy)₂](ClO₄) · H₂O (2a) has been determined. The electrochemical and electronic spectral studies have established that there remain difference in properties and hence difference in intermetallic communication between the diastereoisomeric forms in each case.