Di- and tetranuclear metal complexes with phenoxo bridges: synthesis, structures, and photoluminescent and electroluminescent properties

Dinuclear and tetranuclear copper 2,6-bis(2-hydroxyphenyl)pyridine (H(2)L) complexes Cu2(L)2(py)2 (1) and Cu4(L)4(DMF) (2) were synthesized. The complexes 1 and 2 were characterized by elemental analyses, mass spectrometry, and single-crystal X-ray diffraction analyses. 1 crystallizes in the monoclinic space group P2(1)/n with a = 13.330(2) Angstroms, b = 9.361(1) Angstroms, c = 14.676(1) Angstroms, beta = 100.94(1) degrees, V = 1798.1(3) Angstroms(3), and Z = 2. 2 crystallizes in the monoclinic space group P2(1)/n with a = 13.360(1) Angstroms, b = 14.884(1) Angstroms, c = 15.462(2) Angstroms, beta = 97.50(4) degrees, V = 3048.4(1) Angstroms(3), and Z = 2. Tetranuclear zinc complex Zn4(L)4(py)4 (3) was prepared and characterized by X-ray diffraction. 3 crystallizes in the triclinic space group P with a = 13.770(1) Angstroms, b = 15.465(1) A, c = 16.409(2) Angstroms, alpha = 88.877(9) degrees, beta = 88.035(4) degrees, gamma = 82.956(3) degrees, V = 3465.6(5) Angstroms(3), and Z = 2. The di- and tetranuclear complexes 1-3contain phenoxo bridges. 1 is a dinuclear complex with two Cu(II) centers, two py ligands, and two L ligands, and each L ligand donates its pyridyl ring and one of the phenolate groups to one metal and shares the other phenolate group between both metals, affording a Cu(2)(mu-O)(2) core. 2, in contrast, is a tetranuclear complex with four Cu(II) centers and four L ligands. Two of the L ligands have the same coordination mode as 1, and the other two L ligands donate their pyridyl rings to one metal and share both phenolate groups between four metals, resulting in three four-membered Cu2(mu-O)2 rings, which joined each other and showed great distortion from planarity. 3 is a tetranuclear complex with four Zn(II) centers, four pyridine ligands, and four L ligands, and the L ligands have the same coordination modes as those of 2. Single-crystal X-ray analysis showed that hydrogen-bonding and pi-pi stacking interactions exist in complexes 1 and 2 resulting in two- and three-dimensional molecular arrangements, and the parallel arrangement of the ligand in the crystal of complex 3 resulted in a close inter- and intramolecular pi-pi interactions. Investigation of the crystals, as well as an amorphous thin film and powder of 3, by photoluminescence (PL) allowed the effect of the molecular packing on the emission properties to be elucidated. Furthermore, the electroluminescent (EL) properties of 3 were examined by fabricating a multilayer device with structure of [ITO/NPB/(ZnL)(n)/Alq3/LiF/Al] (NPB = N,N'-bis(alpha-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine, Alq3 = tris(8-hydroxyquinolinato)aluminum).     

Supramolecular assemblies with calix[6]arenes and copper ions: from dinuclear to trinuclear linear arrangements of hydroxo-Cu(II) complexes

Complexation of copper(II) by calix[6]arene-based ligands bearing either two or three N-benzylimidazole coordinating arms under basic conditions has been studied. Whereas the tris(imidazole) derivative stabilizes dicationic 5-coordinate aqua complexes in a mononuclear state with an intracavity bound guest, in the presence of hydroxide ions, the latter undergo dimerization. An X-ray structure revealed decoordination of one imidazole arm and formation of a bis(hydroxo) bridged Cu(II) core with a square-planar geometry for both metal centers sandwiched by two empty calixarene cavities. Upon methanolysis, the dinuclear complex underwent an unexpected rearrangement leading to the clean formation of a trinuclear complex. X-ray diffraction analyses of this novel species revealed a trinuclear core constructed around a central Cu(II) ion that is doubly bridged through either methoxide or hydroxide anions to two Cu(II) ions hold by two calixarene units. The same complex could be directly synthesized by reacting the ligand with copper(II) perchlorate in a 2:3 ratio in the presence of base. In solution, the tetrahydroxo Cu(3) complex was characterized by UV-vis and (1)H NMR spectroscopies and displayed an electron paramagnetic resonance (EPR) signal only below 100 K that accounts for a S = 1/2 fundamental state. Formation of the same di- and trinuclear species was observed with a calix[6]arene-based bis(imidazole) ligand, which demonstrates the generality of the reaction schemes. All these results emphasize the versatility of the calix[6]arene scaffold for the stabilization of metal complexes with various nuclearities.     

Synthesis and characterization of tris(bipyridyl)ruthenium(II)-modified mono-, di-, and trinuclear manganese complexes as electron-transfer models for photosystem II

With the aim of modeling the arrangement of redox-active and photoactive components along the electron-transfer pathway of photosystem II, tetra- to nonanuclear transition metal complexes have been synthesized, comprising one, two, or three manganese ions, oxidizable phenolates, and tris(2,2'-bipyridyl)ruthenium(II)-type units as photosensitizers. These model complexes are considered to be mononuclear ([LnMn](PF6)m), dinuclear ([L1aMnIV2(mu-O)2](PF6)6), or trinuclear ([LnMnIIMnIIMnIILn](PF6)12) with respect to the number of manganese centers present. Electronic coupling between the manganese ions is strongly antiferromagnetic in the case of the di(mu-oxo)-dimanganese compound [L1aMnIV2(mu-O)2](PF6)6, where the "ligand" [H2L1a]4+ consists of two tris(bipyridyl)ruthenium(II)-type units covalentely bound to a bismacrocyclic Me2dtne backbone to which the manganese ions are coordinated via an additional phenolate oxygen (Me2dtne = 1,2-bis(4-methyl-1,4,7-triazacyclononyl)ethane). Weak antiferromagnetic coupling is observed in compounds [LnMnIIMnIIMnIILn](PF6)12, where the three metals are in a linear arrangement (face-sharing octahedral). They are bridged by three phenolate oxygens of each of the deprotonated "ligands" [H3Ln]6+, respectively. Each ligand [H3Ln]6+ (n = 1, 2) consists of a tacn ring with three pendent arm phenols which are each bound to a tris(bipyridyl)ruthenium(II)-type unit (tacn = 1,4,7-triazacyclononane). In these compounds several electron-transfer steps were detected by electrochemical methods which are assigned to different redox processes located at individual electrochemically active components (Mn, Ru, bipyridyl, phenolate). For example, in the "mononuclear" compounds [LnMn](PF6)m (n = 1 or 2) Mn(II), Mn(III), and Mn(IV) are accessible and three Ru(II) centers are reversibly oxidized to Ru(III), and in addition, the coordinated phenolate can be oxidized to a highly reactive, coordinated phenoxyl radical. In several cases very slow heterogeneous electron-transfer rates were observed for redox processes involving the manganese centers.     

Two novel nanoporous supramolecular architectures based on copper(i) coordination polymers with uniform (8, 3) and (8(2)10) nets: in situ formation of tetrazolate ligands

The hydro/solvothermal reactions of Cu(I)/Cu(II) salt, NaN(3), and acetonitrile in water or methanol yield two noninterpenetrated supramolecular networks containing 1D hexagonal and square nanochannels, {[Cu(Mtta)]x0.17H(2)O}(n )(1) and its pseudopolymorph [Cu(Mtta)](n) (2) (Mtta = 5-methyl tetrazolate), involving ligand in-situ formation by cycloaddition of nitriles and azides. The copper(I) centers in both complexes are all bridged by Mtta ligands, forming the different shapes of the cavity. (1) exhibits an unprecedented uniform (8, 3) topological metal network, whereas (2) is a 3-connected (8(2)10) metal net.     

Functional superoxide dismutase mimics. Structural characterization and magnetic exchange interactions of copper(II)-N-substituted sulfonamide dimer complexes

Dinuclear copper(II) complexes with N-substituted sulfonamide ligands as superoxide dismutase (SOD) mimics have been investigated. The new N-(thiazol-2-yl)toluenesulfonamide (Htz-tol) and N-(thiazol-2-yl)naphthalenesulfonamide (Htz-naf) ligands have been prepared and structurally characterized. The complexes derived from these ligands, [Cu(2)(tz-tol)(4)] (1) and [Cu(2)(tz-naf)(4)] (2), have been synthesized, and their crystal structure, magnetic properties, and EPR spectra were studied in detail. In both compounds the metal centers are bridged by four nonlinear triatomic NCN groups. The coordination geometry of the coppers in the dinuclear entity of 1 and 2 is distorted square planar with two N-thiazole and two N-sulfonamido atoms. Magnetic susceptibility data show a strong antiferromagnetic coupling, with -2J = 121.3 cm(-1) for compound 1 and -2J = 104.3 cm(-1) for compound 2. The EPR spectra of the polycrystalline samples of compounds 1 and 2 have been measured at the X- and Q-band frequencies at different temperatures. Above 20 K the spectra are characteristic of S = 1 species with zero-field splitting parameter D = 0.230 cm(-1) for compound 1 and 0.229 cm(-1) for compound 2. The EPR parameters are discussed in terms of the known binuclear structures. The complexes exhibit high SOD activity, as shown by the low IC(50) values obtained with the xanthine/xanthine oxidase/NBT assay: 0.13 microM for compound 1; 0.17 microM for compound 2.     

Synthesis of copper(II) and nickel(II) triazacycloalkane complexes

Summary Copper(II) and nickel(II) complexes of triazacycloalkanes (pqr-cy), with p, q, r = 2–6, have been prepared and characterized by means of electronic and i.r. spectroscopy, and by magnetic measurements. With nickel(II) mononuclear octahedral complexes [Ni(pgr-cy)₂](CI0₄)₂ are formed, but for copper(II) mononuclear octahedral complexes were obtained only for 222-cy and 223-cy. The other ligands gave copper(II) complexes of the type [Cu(pgr-cy)CI]CIO₄, [Cu(pgr-cy)OH]ClO₄, Or [Cu(pgr-cy)CI_1/2OH_1/2]ClO₄. The hydroxy complexes have low magnetic moments and binuclear hydroxy bridged structures are proposed.Ligand names: e.g. p = q = r = 2 is 1,4,7-triazacvclononane     

Trinuclear Zn(II) and Cu(II) homo and heterotrimetallic complexes involving D-glucopyranosyl and biscarboxylate bridging ligands. A substrate binding model of xylose isomerases

Reactions of MCl(2).nH(2)O with N,N'-bis(D-glucopyranosyl)-1,4,7-triazacyclononane ((D-Glc)(2)-tacn), which was formed from D-glucose and 1,4,7-triazacyclononane (tacn) in situ, afforded a series of mononuclear divalent metal complexes with two beta-D-glucopyranosyl moieties, [M((D-Glc)(2)-tacn)Cl]Cl (M = Zn (11), Cu (12), Ni (13), Co (14)). Complexes 11-14 were characterized by analytical and spectroscopic measurements and X-ray crystallography and were found to have a distorted octahedral M(II) center ligated by the pentacoordinate N-glycoside ligand, (beta-D-glucopyranosyl)(2)-tacn, and a chloride anion. Each D-glucose moiety is tethered to the metal center through the beta-N-glycosidic bond with tacn and additionally coordinated via the C-2 hydroxyl group, resulting in a lambda-gauche five-membered chelate ring. When L-rhamnose (6-deoxy-L-mannose) was used instead of D-glucose, the nickel(II) complex with two beta-L-rhamnopyranosyl moieties, [Ni((D-Man)(2)-tacn)(MeOH)]Cl(2) (15), was obtained and characterized by an X-ray analysis. Reactions of 11 (M = Zn) with [Zn(XDK)(H(2)O)] (21) or [Cu(XDK)(py)(2)] (22) (H(2)XDK = m-xylylenediamine bis(Kemp's triacid imide)) yielded homo and heterotrimetallic complexes formulated as [Zn(2)M'((D-Glc)(2)-tacn)(2)(XDK)]Cl(2) (M' = Zn (31), Cu (32)). The similar reactions of 12 (M = Cu) with complex 21 or 22 afforded [Cu(2)M'((D-Glc)(2)-tacn)(2)(XDK)]Cl(2) (M' = Cu (33), Zn (34)). An X-ray crystallographic study revealed that complexes 31 and 34 have either Zn(II)(3) or Cu(II)Zn(II)Cu(II) trimetallic centers bridged by two carboxylate groups of XDK and two D-glucopyranosyl residues. The M...M' separations are 3.418(3)-3.462(3) A (31) and 3.414(1)-3.460(1) A (34), and the M...M'...M angles are 155.18(8) degrees (31) and 161.56(6) degrees (34). The terminal metal ions are octahedrally coordinated by the (D-Glc)(2)-tacn ligand through three nitrogen atoms of tacn, two oxygen atoms of the C-2 hydroxyl groups of the carbohydrates, and a carboxylate oxygen atom of XDK ligand. The central metal ions sit in a distorted octahedral environment ligated by four oxygen atoms of the carbohydrate residues in the (D-Glc)(2)-tacn ligands and two carboxylate oxygen atoms of XDK. The deprotonated beta-D-glucopyranosyl unit at the C-2 hydroxyl group bridges the terminal and central ions with the C-2 mu-alkoxo group, with the C-1 N-glycosidic amino and the C-3 hydroxyl groups coordinating to each metal center. Complexes 31-34 are the first examples of metal complexes in which D-glucose units act as bridging ligands. These structures could be very useful substrate binding models of xylose or glucose isomerases, which promote D-glucose D-fructose isomerization by using divalent dimetallic centers bridged by a glutamate residue.     

Influence of Intramolecular Coordination on the Aggregation of Sodium Phenolate Complexes. X-ray Structures of [NaOC(6)H(4)(CH(2)NMe(2))-2](6) and [Na(OC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4)(HOC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4)](2)

The structural characterization of two new sodium phenolate complexes, containing ortho-amino substituents, enables the influence of intramolecular coordination on the aggregation of sodium phenolate complexes to be determined. Crystals of hexameric [NaOC(6)H(4)(CH(2)NMe(2))-2](6) (1a) are monoclinic, space group P2(1)/c, with a = 11.668(4) ?, b = 18.146(4) ?, c = 14.221(5) ?, beta = 110.76(3) ?, V = 2815.5(16) ?(3), and Z = 2; R = 0.0736 for 2051 reflections with I > 2.0sigma(I). Complex 1a contains a unique Na(6)O(6) core, consisting of two face-fused cubes, with the ortho-amino substituent of each phenolate coordinating to a sodium atom. In addition, two of the phenolate ligands have an eta(2)-arene interaction with an additional sodium atom in the core. Crystals of dimeric [(NaOC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4)(HOC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4)](2) (2b) are triclinic, space group P&onemacr;, with a = 10.0670(8) ?, b = 10.7121(7) ?, c = 27.131(3) ?, alpha = 92.176(8) degrees, beta = 99.928(8) degrees, gamma = 106.465(6) degrees, V = 2752.1(4) ?(3), and Z = 2; R = 0.0766 for 5329 reflections with I > 2.0sigma(I). Dimeric complex 2b contains two phenolate ligands, which bridge the two sodium atoms, each coordinating with one ortho-amino substituent to a sodium atom, while the second available ortho-amino substituent remains pendant. The coordination sphere of each sodium atom is completed by a (neutral) bidentate O,N-coordinated parent phenol molecule. The second ortho-amino substituent of this neutral phenol is involved in a hydrogen bridge with its acidic hydrogen. On the basis of these two new crystal structures and previously reported solid state structures for sodium phenolate complexes, it is shown that the introduction of first one and then two ortho-amino substituents into the phenolate ligands successively lowers the degree of association of these complexes in the solid state. In this process, the basic Na(2)O(2) building block of the molecular structures remains intact.     

Aggregation of [Cu(II)4] building blocks into [Cu(II)8] clusters or a [Cu(II)4]infinity chain through subtle chemical control

Coordination complexes of the ligand H3L [1,3-bis(3-oxo-3-phenylpropionyl)-2-hydroxy-5-methylbenzene] with Cu(II) are reported. Clusters showing various nuclearities or modes of supramolecular organization have been prepared by slightly changing the reaction conditions and have been crystallographically characterized. The reaction of H3L with one equivalent of Cu(OAc)2 in DMF yields the dinuclear complex [Cu2(HL)2(dmf)2] (1). Reaction in MeOH of H3L with an increased amount of metal, in the form of Cu(NO3)2, and excess strong base (nBu4NOH) affords the cluster [Cu8(L)2(OMe)8(NO3)2] (2). Complex 2 is a dimer of two linear [Cu4] arrays bridged by methoxide ligands, where the polynucleating ligand is fully deprotonated. The [Cu4]2 clusters are linked to each other by NO3- bridges to form one-dimensional coordination polymers. The link between [Cu8] units and their relative spatial positioning can be modified by changing the anion of the Cu(II) salt, as demonstrated by the synthesis of the cluster polymers [Cu8(L)2(OMe)8Cl2] (3) and [Cu8(L)(OMe)7.86Br2.14] (4), where only NO3- has been replaced by Cl- or Br-, respectively. Similarly, when ClO4- is used, compound [Cu8(L)2(OMe)8(ClO4)2(MeOH)4] (5) can be isolated. It contains independent [Cu8] units. A slight change in the stoichiometry of the reaction leading to 2 affords the related complex catena-[Cu4(L)(OMe)3(NO3)2(H2O)0.36] (6). This polymer contains essentially the same [Cu4] moiety as 2, albeit organized in a completely different arrangement. Each [Cu4] unit in 6 is linked by OMe- ligands to two such equivalent groups to form an infinite chain. Magnetic susceptibility measurements reveal weak antiferromagnetic exchange between Cu(II) centers in 1 (J = -0.73 cm(-1)) and strong antiferromagnetic coupling within [Cu4] chains in 2, 5, and 6 (most negative J values of -113.8 and -177.3 cm(-1) for 2 and 6, respectively).     

A series of trinuclear Cu(II)Ln(III)Cu(II) complexes derived from 2,6-Di(acetoacetyl)pyridine: synthesis, structure, and magnetism

A series of trinuclear Cu(II)Ln(III)Cu(II) complexes with the bridging ligand 2,6-di(acetoacetyl)pyridine have been prepared by one-pot reaction with Cu(NO(3))(2).3H(2)O and Ln(NO(3))(3).nH(2)O in methanol. X-ray crystallographic studies for all the complexes indicate that two L(2)(-) ligands selectively sandwich two Cu(II) ions with the 1,3-diketonate entities and one Ln(III) ion with the 2,6-acetylpyridine entity to form a trinuclear CuLnCu core bridged by the enolate oxygen atoms. Cryomagnetic properties of the complexes are studied with respect to the electronic structure of the Ln ion.     

Synthesis, spectral and thermal studies of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complex dyes based on hydroxyquinoline moiety

A series of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of azo-compounds containing hydroxyl quinoline moiety have been synthesized and characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic and ESR spectral studies. The results revealed the formation of 1:1 and 1:2 (L:M) complexes. The molar conductance data reveal that the chelates are nonelectrolyte. IR spectra indicate that the azodyes behave as monobasic bidentate or dibasic tetradentate ligands through phenolate or carboxy oxygen, azo N for 1:1 (L:M) complexes beside phenolate oxygen and quinoline N atoms for 1:2 (L:M) complexes. The thermal analyses (TG and DTA) as well as the solid electrical conductivity measurements are also studied. The molecular parameters of the ligands and their metal complexes have been calculated.     

Novel acetate binding modes in [Na2Cu(CH3COO)4(H2O)].H2O

A new copper(II) acetate, [Na(2)Cu(CH(3)COO)(4)(H(2)O)].H(2)O (1), has been crystallized from an aqueous solution containing sodium acetate and copper(II) acetate monohydrate in a 4:1 ratio and the structure determined by X-ray crystallography. 1 crystallizes in the monoclinic space group P2(1)/c, with a = 16.638(3) A, b = 11.781(2) A, c = 15.668(3) A, beta = 90.11(3) degrees, V = 3071.0(11) A(3), and Z = 4. In the asymmetric unit, sodium ions bridge two crystallographically unique square planar [Cu(CH(3)COO)(4)](2-) units to their symmetry-generated neighbors to form corrugated 2D sheets of Na(2)Cu(CH(3)COO)(4), which are held together by H-bonding interactions involving the waters of crystallization. In contrast, the structures of known sodium copper acetates are better described as 3D frameworks. The metal centers are bridged by a number of acetates in novel coordination modes. The square planar Cu(II) geometry generated by oxygen atoms from four different acetates is an unexpected feature given the weak ligand field provided by the acetate ligands.     

Syntheses, crystal structures, and magnetic properties of one-dimensional oxalato-bridged Co(II), Ni(II), and Cu(II) complexes with n-aminopyridine (n = 2-4) as terminal ligand

The reaction of M(ox) x 2H(2)O (M = Co(II), Ni(II)) or K(2)(Cu(ox)(2)) x 2H(2)O (ox = oxalate dianion) with n-ampy (n = 2, 3, 4; n-ampy = n-aminopyridine) and potassium oxalate monohydrate yields one-dimensional oxalato-bridged metal(II) complexes which have been characterized by FT-IR spectroscopy, variable-temperature magnetic measurements, and X-ray diffraction methods. The complexes M(mu-ox)(2-ampy)(2) (M = Co (1), Ni (2), Cu (3)) are isomorphous and crystallize in the monoclinic space group C2/c (No. 15), Z = 4, with unit cell parameters for 1 of a = 13.885(2) A, b = 11.010(2) A, c = 8.755(1) A, and beta = 94.21(2) degrees. The compounds M(mu-ox)(3-ampy)(2).1.5H(2)O (M = Co (4), Ni (5), Cu (6)) are also isomorphous and crystallize in the orthorhombic space group Pcnn (No. 52), Z = 8, with unit cell parameters for 6 of a = 12.387(1), b = 12.935(3), and c = 18.632(2) A. Compound Co(mu-ox)(4-ampy)(2) (7) crystallizes in the space group C2/c (No. 15), Z = 4, with unit cell parameters of a = 16.478(3) A, b = 5.484(1) A, c = 16.592(2) A, and beta = 117.76(1) degrees. Complexes M(mu-ox)(4-ampy)(2) (M = Ni (8), Cu (9)) crystallize in the orthorhombic space group Fddd (No. 70), Z = 8, with unit cell parameters for 8 of a = 5.342(1), b = 17.078(3), and c = 29.469(4) A. All compounds are comprised of one-dimensional chains in which M(n-ampy)(2)(2+) units are sequentially bridged by bis-bidentate oxalato ligands with M.M intrachain distances in the range of 5.34-5.66 A. In all cases, the metal atoms are six-coordinated to four oxygen atoms, belonging to two bridging oxalato ligands, and the endo-cyclic nitrogen atoms, from two n-ampy ligands, building distorted octahedral surroundings. The aromatic bases are bound to the metal atom in cis (1-6) or trans (7-9) positions. Magnetic susceptibility measurements in the temperature range of 2-300 K show the occurrence of antiferromagnetic intrachain interactions except for the compound 3 in which a weak ferromagnetic coupling is observed. Compound 7 shows spontaneous magnetization below 8 K, which corresponds to the presence of spin canted antiferromagnetism.     

A novel hexanuclear mixed oxidation state Cu(II)(4)Cu(I)(2) cluster complex exhibiting weak ferromagnetic exchange

The complex [(PAH)(4)Cu(II)(4)Cu(I)(2)Br(10)] (1) (PAH = picolinamide hydrazone) containing a Cu(II)(4)Cu(I)(2) hexanuclear cluster, with two well-separated Cu(II)(2) dinuclear centers, results from a redox reaction involving a hydrolytically unstable ligand, salicilyl picolinamide hydrazone, and CuBr(2) in aqueous acetonitrile. The Cu(II) centers are axially bridged via long bromine contacts, leading to ferromagnetic exchange (2J = 4.04 cm(-)(1)). Density functional calculations have been carried out, giving a comparable singlet-triplet splitting energy. 1 crystallizes in the triclinic system, space group Ponemacr;, with a = 9.253(3) A, b = 18.159(3) A, c = 7.199(5) A, alpha = 91.31(3) degrees, beta = 107.35(4) degrees, gamma = 104.22(2) degrees, and Z = 2.     

Synthesis, X-ray crystal structures, magnetism, and phosphate ester cleavage properties of copper(II) complexes of N-substituted derivatives of 1,4,7-triazacyclononane

Two new N-substituted derivatives of the 1,4,7-triazacyclononane (tacn) macrocycle, 1-benzyl-4,7-dimethyl-1,4,7-triazacyclononane (L2) and 1,4,7-tris(3-cyanobenzyl)-1,4,7-triazacyclononane (L3), have been prepared and, together with 1,4-dimethyl-1,4,7-triazacyclononane (L1), have been used to synthesize the corresponding hydroxo-bridged binuclear copper (II) complexes, [Cu2(mu-OH)2L2](ClO4)2.xH2O (1 L = L1, x = 0; 2 L = L2, x = 1; 3 L = L3, x = 2). The X-ray crystal structures of all three complexes reveal the presence of [Cu2(mu-OH)2]2+ cores capped by pairs of facially coordinating tacn ligands so that the Cu(II) centers reside in distorted square pyramidal coordination environments. Variable-temperature magnetic susceptibility measurements indicate weak antiferromagnetic coupling (J = -36.4 cm(-1)) between the Cu(II) centers in 1, while the centers in 2 and 3 have been shown to interact ferromagnetically (J = 11.2 and 49.3 cm(-1), respectively). The variation in the strength and sign of these interactions has been rationalized in terms of the differing geometries of the [Cu2(mu-OH)2]2+ cores. The ability of the Cu(II) complexes to cleave phosphate ester bonds has been probed using the model phosphate ester bis(4-nitrophenyl)phosphate (BNPP) at pH 7.4 and a temperature of 50 degrees C. The measured rate constant for 3 (3 x 10(-4) s(-1)) is significantly greater than those previously reported for the Cu(II) complexes of the fully alkylated tacn ligands, Me3tacn and iPr3tacn, which until now have been rated as the most effective tacn-based phosphate ester cleavage agents.     

Mononuclear-dinuclear equilibrium of grafted copper complexes confined in the nanochannels of MCM-41 silica

Following the structural concept of copper-containing proteins in which dinuclear copper centers are connected by hydroxide bridging ligands, a bidentate copper(II) complex has been incorporated into nano-confined MCM-41 silica by a multistep sequential grafting technique. Characterization by a combination of EPR spectroscopy, X-ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, IR spectroscopy , and solid-state (13)C and (29)Si cross-polarization magic-angle spinning (CP-MAS) NMR suggests that dinuclear Cu complexes are bridged by hydroxide and other counterions (chloride or perchlorate ions), similar to the situation for EPR-undetectable [Cu(II)···Cu(II)] dimer analogues in biological systems. More importantly, a dynamic mononuclear-dinuclear equilibrium between different coordination modes of copper is observed, which strongly depends on the nature of the counterions (Cl(-) or ClO(4)(-)) in the copper precursor and the pore size of the silica matrix (the so-called confinement effect). A proton-transfer mechanism within the hydrogen-bonding network is suggested to explain the dynamic nature of the dinuclear copper complex supported on the MCM-41 silica.     

Synthesis, structure, magnetism, and spectroscopic properties of heterobinuclear copper(II)-zinc(II) complexes and their copper(II)-copper(II) analogues in asymmetric ligand environments

Heterobinuclear copper(II)-zinc(II) complexes and their homobinuclear dicopper(II) counterparts (1-4) of two asymmetric ligands (H2L1 and H2L2), based on 2-aminocyclopent-1-ene-1-dithiocarboxylate, are reported. The ligands are capable of providing both donor set and coordination number asymmetry in tandem. Metal centers in these complexes are connected by a micro-alkoxo and a bridging pyrazolate moiety, as confirmed by X-ray structure analyses of 1, 3, and 4. The Cu(1) site in the dicopper complex (1) is square planar and so are the copper sites in the Cu-Zn complexes 3 and 4. The pentacoordinated Zn sites in the latter complexes have distorted TBP geometry (tau = 0.74), while the corresponding Cu site in 1 has a highly distorted square pyramidal structure (tau = 0.54). The Cu...Zn separations in 3 and 4 are 3.3782 and 3.3403 angstroms, respectively, while the Cu...Cu distance in 1 is 3.3687 angstroms. The dicopper complexes are EPR silent at 77 K, in which the copper(II) centers are coupled by strong antiferromagnetic coupling (J = ca. -290 cm(-1)) as confirmed by variable-temperature (4-300 K) magnetic measurements. These compounds (1 and 2) undergo two one-electron reductions and a single step two-electron oxidation at ca. -0.26, -1.40, and 1.0 V vs Ag/AgCl reference, respectively, as indicated by cyclic and differential pulse voltammetry done at subambient temperatures. EPR spectra of 3 and 4 display axial anisotropy at 77 K with the gperpendicular region being split into multiple lines due to N-superhyperfine coupling (AN = 15.3 x 10(-4) cm(-1)). The observed trend in the spin-Hamiltonian parameters, gparallel > gperpendicular > 2.04 and |Aperpendicular| < |Aparallel| approximately (120-150) x 10(-4) cm(-1), indicates a d(x2-y2)-based ground state with tetragonal site symmetry for the Cu(II) center in these molecules.     

Synthesis,structural studies and bio-activity of some metal(II) complexes with glyoxal salicylaldehyde acyldihydrazones

Complexes of the type [M(gssdh)]Cl and [M(gspdh)]Cl, where M?=?Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), Hgssdh?=?glyoxal salicylaldehyde succinic acid dihydrazone and Hgspdh?=?glyoxal salicylaldehyde phthalic acid dihydrazone, have been synthesized and characterized by elemental analyses, molar conductance, magnetic moments, electronic, ESR and IR spectra and X-ray powder diffraction studies. The metal complexes are insoluble in common organic solvents and are 1?:?1 electrolytes. The magnetic moment values and electronic spectra indicate a spin–free octahedral geometry for all Co(II), Ni(II) and Cu(II) complexes. ESR spectral parameters of Cu(II) complexes suggest an elongated tetragonally–distorted octahedral stereochemistry around copper. Both ligands are monobasic hexadentate ligands coordinating through three >C=O, two >C=N– and a deprotonated phenolate group to the metal. X-ray powder diffraction parameters for three of the complexes correspond to an orthorhombic crystal lattice. The complexes show appreciable activity against various fungi and bacteria.     

Varying coordination modes and magnetic properties of copper(II) complexes with diazamesocyclic ligands by altering additional donor pendants on 1,5-diazacyclooctane

A series of new diazamesocyclic ligands based on a diazamesocycle, 1,5-diazacyclooctane (DACO), functionalized by additional donor groups--1,5-bis(N-1-methylimidazol-2-ylmethyl)-1,5- diazacyclooctane (L1), 1-(2-hydroxybenzyl)-1,5-diazacyclooctane (HL2), 1,5-bis(2-hydroxybenzyl)-1,5-diazacyclooctane (H2L3), and 1-(N-1-methylimidazol-2-ylmethyl)-1,5-diazacyclooctane (L4)--and their Cu(II) complexes have been synthesized and characterized. Single-crystal X-ray diffraction analysis of the four Cu(II) complexes revealed that L1 forms a five-coordinate mononuclear complex, HL2 a N3- mu-bridged binuclear complex, H2L3 an oxygen mu-bridged trinuclear complex, and L4 a one-dimensional zigzag coordination polymeric complex with Cu(II). [CuL1ClO4](ClO4) (I): a = 12.194(2) A, b = 13.351(3) A, c = 14.473(3) A, beta = 107.10(3) degrees, Z = 4. [CuL2(N3)]2 (II): a = 8.1864(6) A, b = 18.141(2) A, c = 9.3307(7) A, beta = 103.662(6) degrees, Z = 2. [Cu3(L3)2Cl2] (III): a = 10.7296(13) A, b = 13.7707(17) A, c = 13.5523(17) A, beta = 106.350(3) degrees, Z = 2. ([CuL4Cl]2ClO4) infinity (IV): a = 7.279(1) A, b = 23.695(5) A, c = 19.308(4) A, beta = 100.28(3) degrees, Z = 8. All four complexes crystallize in the monoclinic crystal system with the P2(1)/c space group, and each Cu(II) center coordinated with DACO is pentacoordinated with a distorted square-pyramidal or trigonal-bipyrimidal coordination environment. In complex IV, the binuclear cation unit [CuL4Cl]2(2+) constitutes the fundamental building block of an infinite alternating zigzag chain structure, and the binuclear unit contains two types of geometries around the Cu(II) centers: the Cu(1) center is a distorted square-pyramidal environment, while the Cu(2) is a distorted trigonal-bipyramidal coordination environment. To the best of our knowledge, this is the first Cu(II) complex of a diazamesocyclic ligand with an infinite polymeric structure. The magnetic properties of complexes II, III, and IV have been investigated by variable-temperature magnetic susceptibility measurements in the solid state. The obtained parameters are 2J = 2.06 cm-1 (II), -345.56 cm-1 (III), and -2.60 cm-1 (IV), which differ greatly from ferromagnetic to weak and strong antiferromagnetic coupling. These results unequivocally indicate that the nature of the pendant arms is a key factor governing the structure and properties of the complexes; therefore, the coordination modes and properties of the metal complexes of a diazamesocycle can be controlled by altering the pendant donors on it. Magneto-structural correlation has been precisely analyzed, and the solution properties of these complexes have also been described.