Systematic studies on 3d-3d and 3d-4f multimetallic complexes with interesting magnetic and/or luminescent properties

324 p.

Feature-point detection using distance transforms: Application to tracking tropical convective complexes

The identification, tracking, and statistical analysis of tropical convective complexes using satellite imagery is explored in the context of identifying feature points suitable for tracking. The feature points are determined based on the shape of complexes using the distance transform technique. This approach has been applied to the determination feature points for tropical convective complexes identified in a time series of global cloud imagery. The feature points are used to track the complexes, and from the tracks statistical diagnostic fields are computed. This approach allows the nature and distribution of organized deep convection in the Tropics to be explored.

Metal complexes of a tetraazacyclophane: solution and molecular modelling studies

An alternative synthetic approach to yield the compound 2,3,5,6,8,9,11,14-octahydrobenzo[1][ 1,4,7,10]tetraazacyclotetradecine (bz[14]N-4) is presented. The protonation constants of bz[14]N-4 and the stability constants of its complexes with Ni2+, Cu2+, Zn2+, Cd2+, Pb2+ were determined in H2O at 25degreesC with ionic strength 0.10 mol dm(-3) in KNO3 and they were compared with structurally related macrocycles cyclam (1,4,8,11-tetraazacyclotetradecane) and cyclen (1,4,7,10-tetraazacyclododecane). These studies indicate that only 1 : 1 ( M : L) species are formed in solution, and the ligand exhibits a high affinity for larger ions such as Cd2+ and Pb2+. The X-ray study of [bz[14]N4H3](3+) shows that an inclusion compound with a chloride counter-anion is formed through NH...Cl hydrogen bonds. Spectroscopic data in solution ( electronic and NMR spectra) showed that the macrocycle adopts a planar arrangement upon metal complexation. Molecular mechanics calculations reveal that in spite of the presence of the benzene ring in the macrocyclic framework this ligand can encapsulate metal ions with different stereo-electronic sizes in square planar arrangements. Our results indicate that the presence of the benzene ring in the backbone of the bz[14]N-4 confers a coordination behaviour intermediate between that of cyclam and cyclen.

Copper complexes of new benzodioxotetraaza macrocycles with potential applications in nuclear medicine

Two novel benzodioxotetraaza macrocycles [2,9-dioxo-1,4,7,10-tetraazabicyclo[10.4.0]1,11-hexadeca-1(11),13,15-triene (H(2)L1) and 2,10-dioxo-1,4,8,11-tetraazabicyclo[11.4.0]1,12-heptadeca-1(12),14,16-triene (H(2)L2)] were synthesized by a [1 + 1] crablike cyclization. The protonation constants of both ligands were determined by H-1 NMR titration and by potentiometry at 25.0 degrees C in 0.10 M ionic strength in KNO3. The latter method was also used to ascertain the stability constants of their copper(II) complexes. These studies showed that the CuL1 complex has a much lower thermodynamic stability than the CuL2, and the H(2)L2 displays an excellent affinity for copper(II), due to the good fit of copper(II) into its cavity. The copper complexes of the novel ligands were characterized by electronic spectroscopy in solution and by crystal X-ray diffraction. These studies indicated that the copper center in the CuL1 complex adopts a square-pyramidal geometry with the four nitrogen atoms of the macrocycle forming the equatorial plane and a water molecule at axial position, and the copper in the CuL2 complex is square-planar. Several labeling conditions were tested, and only H(2)L2 could be labeled with Cu-67 efficiently (> 98%) in mild conditions (39 degrees C, 15 min) to provide a slightly hydrophilic radioligand (log D = -0.19 +/- 0.03 at pH 7.4). The in vitro stability was studied in the presence of different buffers or with an excess of diethylenetriamine-pentaethanoic acid. Very high stability was shown under these conditions for over 5 days. The incubation of the radiocopper complex in human serum showed 6% protein binding.

Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiC CC6F5 and RuCl(dppe)Cp'[Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C CC6F5)(dppe)Cp'[Cp' = Cp (2); Cp* (3)], which are related to the known compound Ru(C CC6F5)(PPh3)(2)Cp (1). Treatment of Me3SiC CC6F5 with Pt-2(mu-dppm)(2)Cl-2 in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt-2(mu-dppm)(2)(C CC6F5)(2) (4). The Pd(0)/Cu(I)-catalysed reactions between Au(C CC6F5)(PPh3) and Mo( CBr)(CO)(2) Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co-3(mu(3)-CBr)(mu-dppm)(CO)(7) or IC CFc [Fc = (eta(5)-C5H4)FeCp] afford Mo( CC CC6F5)(CO)(2)Tp* (5), Co-3(mu 3-CC CC6F5)(mu-dppm)(CO)(7) (6) and FcC CC CC6F5 (7), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC C}(2)C6F4 [(PP)Cp'=(PPh3)(2)Cp (8); (dppe)Cp (9); (dppe)Cp* (10)] are prepared from 1,4-(Me3SiC C)(2)C6F4 in a manner similar to that described for the monoruthenium complexes 1-3. The non-fluorinated complexes 1,4-{Cp'(PP)RuC C}(2)C6H4 [(PP)Cp' = (PPh3)(2)Cp (11); ( dppe) Cp (12); ( dppe) Cp* (13)], prepared for comparison, are obtained from 1,4-(Me3SiC C)(2)C6H4. Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes 2-3 and 8-13, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes 1, 2, 3, 6 and 10.

Dinuclear complexes of M-II thiocyanate (M = Ni and Cu) containing a tridentate Schiff-base ligand: synthesis, structural diversity and magnetic properties

A dinuclear Ni-II complex, [Ni-2(L)(2)(H2O)(NCS)(2)]center dot 3H(2)O (1) in which the metal atoms are bridged by one water molecule and two mu(2)-phenolate ions, and a thiocyanato-bridged dimeric Cull complex, [Cu(L)NCS](2) (2) [L = tridentate Schiff-base ligand, N-(3-aminopropyl)salicylaldimine, derived from 1:1 condensation of salicylaldehyde and 1,3-diaminopropane], have been synthesized and characterized by IR and UV/Vis spectroscopy, cyclic voltammetry and single-crystal X-ray diffraction studies. The structure of 1 consists of dinuclear units with crystallographic C-2 symmetry in which each Ni-II atom is in a distorted octahedral environment. The Ni-O distance and the Ni-O-Ni angle, through the bridged water molecule, are 2.240(11) angstrom and 82.5(5)degrees, respectively. The structure of 2 consists of dinuclear units bridged asymmetrically by di-mu(1,3)-NCS ions; each Cull ion is in a square-pyramidal environment with tau = 0.25. Variable-temperature magnetic susceptibility studies indicate the presence of dominant ferromagnetic exchange coupling in complex 1 with J = 3.1 cm(-1), whereas complex 2 exhibits weak antiferromagnetic coupling between the Cu-II centers with J = -1.7 cm(-1). ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Rhodium assisted C-H activation of N-(2 '-hydroxyphenyl)benzaldimines. Synthesis, structure and electrochemical properties of a group of organorhodium complexes

Reaction of a group of N-(2'-hydroxyphenyl)benzaldimines, derived from 2-aminophenol and five para-substituted benzaldehydes (the para substituents are OCH3, CH3, H, Cl and NO2), with [Rh(PPh3)(3)Cl] in refluxing toluene in the presence of a base (NEW afforded a family of organometallic complexes of rhodium(III). The crystal structure of one complex has been determined by X-ray crystallography. In these complexes the benzaldimine ligands are coordinated to the metal center, via dissociation of the phenolic proton and the phenyl proton at the ortho position of the phenyl ring in the imine fragment, as dianionic tridentate C,N,O-donors, and the two PPh3 ligands are trans. The complexes are diamagnetic (low-spin d(6), S = 0) and show intense MLCT transitions in the visible region. Cyclic voltammetry shows a Rh(III)-Rh(IV) oxidation within 0.63-0.93 V vs SCE followed by an oxidation of the coordinated benzaldimine ligand. A reduction of the coordinated benzaldimine is also observed within -0.96 to -1.04 V vs SCE. Potential of the Rh(Ill)-Rh(IV) oxidation is found to be sensitive to the nature of the para-substituent. (c) 2006 Elsevier B.V. All rights reserved.

1-(2 '-pyridylazo)-2-naphtholate complexes of ruthenium: synthesis, characterization, and DNA binding properties

Reaction of 1-(2'-pyridylazo)-2 -naphthol (Hpan) with [Ru(dmso)(4)Cl-2] (dmso=dimethylsulfoxide), [Ru(trpy)Cl-3] (trpy=2,2',2 ''-terpyridine), [Ru(bpy)Cl-3] (bpy=2,2'-bipyridine) and [Ru(PPh3)(3)Cl-2] in refluxing ethanol in the presence of a base (NEt3) affords, respectively, the [Ru(pan)(2)], [Ru(trpy)(pan)](+) (isolated as perchlorate salt), [Ru(bpy)(pan)Cl] and [Ru(PPh3)(2)(pan)Cl] complexes. Structures of these four complexes have been determined by X-ray crystallography. in each of these complexes, the pan ligand is coordinated to the metal center as a monoanionic tridentate N,N,O-donor. Reaction of the [Ru(bpy)(pan)Cl] complex with pyridine (py) and 4-picoline (pic) in the presence of silver ion has yielded the [Ru(bpy)(pan)(py)](+) and [Ru(bpy)(pan)(pic)](+) complexes (isolated as perchlorate salts), respectively. All the complexes are diamagnetic (low-spin d(6), S = 0) and show characteristic H-1 NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a Ru(II)-Ru(III) oxidation on the positive side of SCE. Except in the [Ru(pan)(2)] complex, a second oxidative response has been observed in the other five complexes. Reductions of the coordinated ligands have also been observed on the negative side of SCE. The [Ru(trpy)(pan)]ClO4, [Ru(bpy)(pan)(py)]ClO4 and [Ru(bpy) (pan)(pic)]ClO4 complexes have been observed to bind to DNA, but they have not been able to cleave super-coiled DNA on UV irradiation. (c) 2008 Elsevier Ltd. All rights reserved.

Anion-directed synthesis of metal-organic frameworks based on 2-picolinate Cu(II) complexes: a ferromagnetic alternating chain and two unprecedented ferromagnetic fish backbone chains

Three new polynuclear copper(II) complexes of 2-picolinic acid (Hpic), {[Cu-2(pic)(3)(H2O)]ClO4}(n) (1), {[Cu-2(pic)(3)(H2O)]BF4}(n) (2), and [Cu-2(pic)3(H2O)(2)(NO3)](n) (3), have been synthesized by reaction of the "metalloligand" [Cu-(pic)(2)] with the corresponding copper(II) salts. The compounds are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. Compounds 1 and 2 are isomorphous and crystallize in the triclinic system with space group P (1) over bar, while 3 crystallizes in the monoclinic system with space group P2(1)/n. The structural analyses reveal that complexes 1 and 2 are constructed by "fish backbone" chains through syn-anti (equatorial-equatorial) carboxylate bridges, which are linked to one another by syn-anti (equatorial-axial) carboxylate bridges, giving rise to a rectangular grid-like two-dimensional net. Complex 3 is formed by alternating chains of syn-anti carboxylate-bridged copper(II) atoms, which are linked together by strong H bonds involving coordinated nitrate ions and water molecules and uncoordinated oxygen atoms from carboxylate groups. The different coordination ability of the anions along with their involvement in the H-bonding network seems to be responsible for the difference in the final polymeric structures. Variable-temperature (2-300 K) magnetic susceptibility measurement shows the presence of weak ferromagnetic coupling for all three complexes that have been fitted with a fish backbone model developed for 1 and 2 (J = 1.74 and 0.99 cm(-1); J' = 0.19 and 0.25 cm(-1), respectively) and an alternating chain model for 3 (J = 1.19 cm(-1) and J' = 1.19 cm(-1)).

Dinuclear copper and zinc complexes of a hexaazamacrocycle containing p-xylyl spacers and bridging anions: theoretical and spectroscopic studies

The hexaazamacrocycle 7,22-dimethyl-3,7,11,18,22,26-hexaazatricyclo[26.2.2.2(13,16)] tetratriaconta-1(30), 13,15,28,31,33- hexaene (Me-2[30] pbz(2)N(6)) was synthesized and characterised by single crystal X-ray diffraction. The macrocycle adopts a conformation with the two aromatic rings almost parallel at a distance of ca. 4.24 Angstrom, but displaced relative to each other by ca. 1.51 Angstrom. The protonation constants of this compound and the stability constants of its complexes with Cu2+ and Zn2+, were determined in water - methanol (9 : 1 v/v) at 25 degreesC with ionic strength 0.10 mol dm(-3) in KCl. The potentiometric and spectroscopic studies (NMR of zinc, cadmium and lead complexes, and EPR of the copper complexes) indicate the formation of only dinuclear complexes. The association constants of the dinuclear copper complex with anions ( thiocyanate, terephthalate and glyphosate) and neutral molecules (1,4-benzenedimethanol, p-xylylenediamine and terephthalic acid) were determined at 20 degreesC in methanol. The structural preferences of this ligand and of its dinuclear copper(II) complex with a variety of bridging ligands were evaluated theoretically by molecular mechanics calculations (MM) and molecular dynamics (MD) using quenching techniques.

Dicopper(II) complexes of a new di-para-xylyldioxatetraazamacrocycle and cascade species with dicarboxylate anions: thermodynamics and structural properties

The new dioxatetraazamacrocycle (L-1) was synthesized by a 2 + 2 condensation and characterized. Stability constants of its copper(II) complexes were determined by spectrophotometry in DMSO at 298.2 K in 0. 10 mol dm(-3) KClO4. Mainly dinuclear complexes are formed and the presence of mononuclear species is dependent on the counterion (Cl- or ClO4-). The association constants of the dinuclear copper(II) complexes with dicarboxylate anions [oxalate (oxa(2-)), malonate (mal(2-)), succinate (suc(2-)), and glutarate (glu(2-))] were also determined by spectrophotometry at 298.2 K in DMSO, and it was found that values decrease with an increase of the alkyl chain between the carboxylate groups. X-Band EPR spectra of the dicopper(II) complexes and of their cascade species in frozen DMSO exhibit dipole-dipole coupling, and their simulation, together with their UV-vis spectra, showed that the copper centres of the complexes in solution had square pyramidal geometries though with different distortions. From the experimental data, it was also possible to predict the Cu...Cu distances, the minimum being found at 6.4 angstrom for the (Cu2LCl4)-Cl-1 complex and then successively this distance slightly increases when the chloride anions are replaced by dicarboxylate anions, from 6.6 angstrom for oxa(2-) to 7.8 for glu(2-). The crystal structures of the dinuclear copper cascade species with oxa(2-) and suc(2-) were determined and showed one anion bridging both copper centres and Cu...Cu distances of 5.485(7) angstrom and 6.442(8) angstrom, respectively.

Structural study of BSA/poly(ethylene glycol) lipid conjugate complexes

In this work we report the structural characteristics of bovine serum albumin/poly(ethylene glycol) lipid conjugate (BSA/PEG(2000)-PE) complexes under physiological conditions (37 degrees C and pH 7.4) for particular fractions of BSA to PEG-lipid concentration, CBSA/C-PEG2000-PE. Ultraviolet fluorescence spectroscopy (UV) results shown that PEG(2000)-PE is associated to BSA, leading to;protein unfolding for fixed C-BSA = 0.01 wt % and variable C-PEG2000-PE = 0.0015-0.6 wt %. Tryptophan groups on the BSA surface are in contact with the PEG-lipid at C-PEG2000-PE = 0.0015 wt %, while they are exposed to water at C-PEG2000-PE (>)0.0015 wt %. Dynamic and static light scattering (DLS and SLS) and small-angle neutron scattering (SANS) point out the existence of individual BSAIPEG-lipid complexes in the system for fixed C-BSA = 1 wt % and variable C-PEG2000-PE = 0.15-2 wt %. DLS shows that there is only one BSA molecule per protein/PEG-lipid complex, while SLS shows that the PEG-lipid associates to the BSA without promoting aggregation between adjacent protein/ polymer-lipid conjugate complexes. SANS was used to show that BSA/PEG(2000)-PE complexes adopt an oblate ellipsoidal shape. Partially unfolded BSA is contained in the core of the oblate ellipsoid, which is surrounded by an external shell containing the PEG(2000)-PE.

Extended-chain, multinuclear transition metal complexes bridged by cyanodiazenido(1-), [N=N-C=N](-), ligands

Extended-chain complexes containing multiple transition metal centres linked by conjugated mu-cyanodiazenido(1-) ligands [N= N-C N]-have been obtained by reaction of trans-[BrW(dppe)(2)(N2CN)], 1, [dppe = 1,2-bis(diphenylphosphino) ethane] with dirhodium(II) tetra-acetate, bis(benzonitrile) palladium(II) dichloride, and bis(aqua) M(II) bis(hexa. uoroacetylacetonate) (M = Mn, Ni, Cu, Zn): stronger Lewis acids such as tetrakis(acetonitrile) palladium(II) tetra. uoroborate and boron trifl. uoride promote hydrolysis of complex 1, leading to the isolation of a novel carbamoylhydrazido(2-) complex, trans-[BrW(dppe) 2(N2HC=ONH2)](+)[BF4](-).

Synthesis, characterization, and anion selectivity of copper(II) complexes with a tetradentate Schiff base ligand

A new mononuclear Cu(II) complex, [CuL(ClO4)(2)] (1) has been derived from symmetrical tetradentate di-Schiff base, N,N'-bis-(1-pyridin-2-yl-ethylidene)-propane-1,3-diamine (L) and characterized by X-ray crystallography. The copper atom assumes a tetragonally distorted octahedral geometry with two perchlorate oxygens coordinated very weakly in the axial positions. Reactions of I with sodium azide, ammonium thiocyanate or sodium nitrite solution yielded compounds [CuL(N-3)]ClO4 (2), [CuL(SCN)ClO4 (3) or [CuL(NO2)]-ClO4 (4), respectively, all of which have been characterized by X-ray analysis. The geometries of the penta-coordinated copper(H) in complexes 2-4 are intermediate between square pyramid and trigonal bipyramid (tbp) having the Addition parameters (tau) 0.47, 0.45 and 0.58, respectively. In complex 4, the nitrite ion is coordinated as a chelating ligand and essentially both the 0 atoms of the nitrite occupy one axial site. Complex 1 shows distinct preference for the anion in the order SCN- > N-3(-) > NO2- in forming the complexes 24 when treated with a SCN-/N-3(-)/NO2- mixture. Electrochemical electron transfer study reveals (CuCuI)-Cu-II reduction in acetonitrile solution. (c) 2006 Elsevier B.V.. All rights reserved.

Methylene spacer-regulated structural variation in cobalt(II/III) complexes with bridging acetate and Salen- or Salpn-type Schiff-base ligands

Two linear, trinuclear mixed-valence complexes, [Co-II{(mu-L-1)(mu-OAc)Co-III (OAc)}(2)] (1) and [Co-II(mu-L-2) (mu-OAc)Co-III(OAc)}(2)] (2) and two mononuclear Con' complexes [Co-III{L-3)(OAc)] (3), and [Co-III {L-4}(OAc)] (4) were prepared and the molecular structures of 1, 2 and 4 elucidated on the basis of X-ray crystallography [OAc = Acetate ion, H2L1 = H(2)Salen 1,6-bis(2-hydroxyphenyl)-2,5-diazahexa-1,5-diene, H2L2 H2Me2-Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene, H2L3 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta1,6-diene, H2L4 = H(2)Me(2)Salpn = 2,8-bis(2-hydroxyphenyl)3,7-diazanona-2,7-dienel. In complexes I and 2, the acetate groups show both monodentate and bridging bidentate coordination modes, whereas chelating bidentate acetate is present in 4. The terminal (CoN2O4)-N-III centres in 1 and 2 exhibit uniform facial arrangements of both non-bridged N2O and bridging O-3 donor sets and the Co-II centre is coordinated to six (four phenoxo and two acetato) oxygen atoms of the bridging ligands. The effective magnetic moment at room temperature corresponds to the presence of high-spin Coll in both 1 and 2. The complexes 1 and 2 are thus Co-III(S = 0)Co-II(S = 3/2)-Co-II(S = 0) trimers. Complexes 3 and 4 are monomeric and diamagnetic containing low-spin Co-III(S = 0) with chelating tetradentate Schiff base and bidentate acetate. Calculations based on DFT rationalise the formation of trinuclear or monomiclear complexes. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).