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Helen Stoeckli-Evans

Publications and source records attributed to Helen Stoeckli-Evans.

At least 19 recordsLinked to original sources
PubMed2006

Structural and magnetic diversity in cyano-bridged bi- and trimetallic complexes assembled from cyanometalates and [M(rac-CTH)]n+ building blocks (CTH = d,l-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane).

Seven new cyano-bridged heterometallic systems have been prepared by assembling [M'(rac-CTH)]n+ complexes (M' = CrIII, NiII, CuII), which have two cis available coordination positions, and [M(CN)6]3- (M = FeIII, CrIII) and [Fe(CN)2(bpy)2]+ cyanometalate building blocks. The assembled systems, which have been characterized by X-ray crystallography and magnetic investigations, are the molecular squares (meso-CTH-H2)[{Ni(rac-CTH)}2{Fe(CN)6)}2].5H2O (2) and [{Ni(rac-CTH)}2{Fe(CN)2(bpy)2}2](ClO4)4.H2O (5), the bimetallic chain [{Ni(rac-CTH)}2{Cr(CN)6)}2Ni(meso-CTH)].4H2O (3), the trimetallic chain [{Ni(rac-CTH)}2{Fe(CN)6)}2Cu(cyclam)]6H2O (4), the pentanuclear complexes [{Cu(rac-CTH}3{Fe(CN)6}2].2H2O (6) and [{Cu(rac-CTH)}3{Cr(CN)6)}2].2H2O (7), and the dinuclear complex [Cr(rac-CTH)(H2O)Fe(CN)6].2H2O (8). With the exception of 5, all compounds exhibit ferromagnetic interaction between the metal ions (JFeNi = 12.8(2) cm-1 for 2; J1FeCu= 13.8(2) cm-1 and J2FeCu= 3.9(4) cm-1 for 6; J1CrCu= 6.95(3) cm-1 and J2CrCu= 1.9(2)cm-1 for 7; JCrFe = 28.87(3) cm-1 for 8). Compound 5 exhibits the end of a transition from the high-spin to the low-spin state of the octahedral FeII ions. The bimetallic chain 3 behaves as a metamagnet with a critical field Hc = 300 G, which is associated with the occurrence of week antiferromagnetic interactions between the chains. Although the trimetallic chain 4 shows some degree of spin correlation along the chain, magnetic ordering does not occur. The sign and magnitude of the magnetic exchange interaction between CrIII and FeIII in compound 8 have been justified by DFT type calculations.

Journal Article↗
PubMed2006

rac-(Z)-Ethyl 2-bromo-2-[(3R,5R)-3-bromo-5-methyltetrahydrofuran-2-ylidene]acetate.

In the title compound, C9H12Br2O3, a (tetrahydrofuran-2-ylidene)acetate, the double bond has the Z form. In the tetrahydrofuran group, the relative configuration of the Br atom in the 3-position and the methyl group in the 5-position is anti. The compound crystallizes with two independent molecules per asymmetric unit and, in the crystal structure, the individual molecules are linked to their symmetry-equivalent molecules by C-H...O hydrogen bonds, so forming centrosymmetric hydrogen-bonded dimers.

Journal Article↗
PubMed2006

The incommensurately modulated structure of a tricyclic natural-product-like compound of empirical formula C22H20O3.

3,4-Diphenyl-2a,5a,6,7,8,8a,8b-heptahydro-furo[4,3,2-de]chromen-2-one (1) was prepared as part of a project aimed at the synthesis of polycyclic natural-product-like scaffolds. X-ray analysis of crystals grown from ethanol revealed an incommensurately modulated structure. Data include main and satellite reflections up to second order. The modulation vector was refined using the NADA program. The modulated character of the structure of the organic compound C(22)H(20)O(3) is interpreted in terms of the intermolecular C-H...O hydrogen bonds and close-contact approximation.

Benzopyrans↗
PubMed2006

Novel 3D, 2D, and 0D first-row coordination compounds with 4,4'-bipyridine-N,N'-dioxide incorporating sulfur-containing anions.

The reaction of M(S2O6) (M = Cu(II), Ni(II), and Co(II)) with 4,4'-bipyridine-N,N'-dioxide (bpdo) results in the formation of novel 3D, 2D, and mononuclear complexes. Complex 1, {[Cu(H2O)(bpdo)2](S2O6)(H2O)}n, is a 2-D wavelike polymer with the Cu(II) ion located on a 2-fold axis and having a distorted square-pyramidal coordination sphere. With Co(II) and Ni(II), 3-D complexes, {[M(bpdo)3](S2O6)(C2H5OH)7}n [M = Co(II) (2), Ni(II) (3)], were obtained. The metal atoms are situated on centers of symmetry and have octahedral environments coordinated to six bpdo molecules. The same reaction in aqueous solution with a metal/ligand ratio of 1:1 results in the formation of mononuclear complexes, {[M(bpdo)(H2O)5](SO4)(H2O)2} [M = Co(II) (4), Ni(II) (5)], accompanied by the decomposition of the dithionate anions S2O6(2-) to sulfate anions SO4(2-).

Journal Article↗
PubMed2006

Atropisomeric discrimination in new Ru(II) complexes containing the C(2)-symmetric didentate chiral phenyl-1,2-bisoxazolinic ligand.

A new family of Ru(II) complexes containing the tridentate meridional 2,2':6',2''-terpyridine (trpy) ligand, a C(2)-symmetric didentate chiral oxazolinic ligand 1,2-bis[4'-alkyl-4',5'-dihydro-2'-oxazolyl]benzene (Phbox-R, R = Et or iPr), and a monodentate ligand, of general formula [Ru(Y)(trpy)(Phbox-R)](n+) (Y = Cl, H(2)O, py, MeCN, or 2-OH-py (2-hydroxypyridine)) have been prepared and thoroughly characterized. In the solid state the complexes have been characterized by IR spectroscopy and by X-ray diffraction analysis in two cases. In solution, UV/Vis, cyclic voltammetry (CV), and one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy techniques have been used. We have also performed density functional theory (DFT) calculations with these complexes to interpret and complement experimental results. The oxazolinic ligand Phbox-R exhibits free rotation along the phenyloxazoline axes. Upon coordination this rotation is restricted by an energy barrier of 26.0 kcal mol(-1) for the case of [Ru(trpy)(Phbox-iPr)(MeCN)](2+) thus preventing its potential interconversion. Furthermore due to steric effects the two atropisomers differ in energy by 5.7 kcal mol(-1) and as a consequence only one of them is obtained in the synthesis. Subtle but important structural effects occur upon changing the monodentate ligands that are detected by NMR spectroscopy in solution and interpreted by using their calculated DFT structures.

Journal Article↗
PubMed2006

Structures, spectra, and DNA-binding properties of mixed ligand copper(II) complexes of iminodiacetic acid: the novel role of diimine co-ligands on DNA conformation and hydrolytic and oxidative double strand DNA cleavage.

The coordination geometry around copper(II) in [Cu(imda)(phen)(H2O)] (1) (H2imda = iminodiacetic acid, phen = 1,10-phenanthroline) is described as distorted octahedral while those in [Cu(imda)(5,6-dmp)] (2) (5,6-dmp = 5,6-dimethyl-1,10-phenanthroline) and [Cu(imda)(dpq)] (3) (dpq = dipyrido-[3,2-d:2',3'-f]-quinoxaline) as trigonal bipyramidal distorted square-based pyramidal with the imda anion facially coordinated to copper(II). Absorption spectral (Kb: 1, 0.60+/-0.04x10(3); 2, 3.9+/-0.3x10(3); 3, 1.7+/-0.5x10(4) M(-1)) and thermal denaturation studies (deltaTm: 1, 5.70+/-0.05; 2, 5.5+/-10; 3, 10.6+/-10 degrees C) and viscosity measurements indicate that 3 interacts with calf thymus DNA more strongly than 1 and 2. The relative viscosities of DNA bound to 1 and 3 increase while that of DNA bound to 2 decreases indicating formation of kinks or bends and/or conversion of B to A conformation as revealed by the decrease in intensity of the helicity band in the circular dichroism spectrum of DNA. While 1 and 3 are bound to DNA through partial intercalation, respectively, of phen ring and the extended planar ring of dpq with DNA base stack, the complex 2 is involved in groove binding. All the complexes show cleavage of pBR322 supercoiled DNA in the presence of ascorbic acid with the cleavage efficiency varying in the order 3 > 1 > 2. The highest oxidative DNA cleavage of dpq complex is ascribed to its highest Cu(II)/Cu(I) redox potential. Oxidative cleavage studies using distamycin reveal minor groove binding for the dpq complex but a major groove binding for the phen and 5,6-dmp complexes. Also, all the complexes show hydrolytic DNA cleavage activity in the absence of light or a reducing agent with cleavage efficiency varying in the order 1 > 3 > 2.

Binding, Competitive↗
PubMed2006

Interaction of rac-[Ru(5,6-dmp)3]2+ with DNA: enantiospecific DNA binding and ligand-promoted exciton coupling.

The X-ray crystal structure of the complex rac-[Ru(5,6-dmp)(3)]Cl(2) (5,6-dmp = 5,6-dimethyl-1,10-phenanthroline) reveals a distorted octahedral coordination geometry with the Ru-N bond distances shorter than in its phen analogue. Absorption spectral titrations with CT DNA reveal that rac-[Ru(5,6-dmp)(3)](2+) interacts (K(b), (8.0 +/- 0.2) x 10(4) M(-1)) much more strongly than its phen analogue. The emission intensity of the 5,6-dmp complex is dramatically enhanced on binding to DNA, which is higher than that of the phen analogue. Also, interestingly, time-resolved emission measurements on the DNA-bound complex shows biexponential decay of the excited states with the lifetimes of short- and long-lived components being higher than those for the phen analogue. The CD spectral studies of rac-[Ru(5,6-dmp)(3)](2+) bound to CT DNA provide a definite and elegant evidence for the enantiospecific interaction of the complex with B-form DNA. Competitive DNA binding studies using rac-[Ru(phen)(3)](2+) provide support for the strong binding of the complex with DNA. The Delta-enantiomer of rac-[Ru(5,6-dmp)(3)](2+) binds specifically to the right-handed B-form of poly d(GC)(12) at lower ionic strength (0.05 M NaCl), and the Lambda-enantiomer binds specifically to the left-handed Z-form of poly d(GC)(12) generated by treating the B-form with 5 M NaCl. The strong electronic coupling of the DNA-bound complex with the unbound complex facilitates the change in its enantiospecificity upon changing the conformation of DNA. The (1)H NMR spectra of rac-[Ru(5,6-dmp)(3)](2+) bound to poly d(GC)(12) reveal that the complex closely interacts most possibly in the major grooves of DNA. Electrochemical studies using ITO electrode show that the 5,6-dmp complex stabilizes CT DNA from electrocatalytic oxidation of its guanine base more than the phen analogue does.

Binding Sites↗
PubMed2006

Bioactive diterpenes from the fruits of Detarium microcarpum.

A fruit pulp extract of Detarium microcarpum showed inhibition of the growth of the plant pathogenic fungus Cladosporium cucumerinum and of the enzyme acetylcholinesterase, implicated in Alzheimer's disease. Fractionation of this extract led to the isolation of four new clerodane diterpenes, 3,4-epoxyclerodan-13E-en-15-oic acid (1), 5alpha,8alpha(2-oxokolavenic acid) (2), 3,4-dihydroxyclerodan-13E-en-15-oic acid (4), and 3,4-dihydroxyclerodan-13Z-en-15-oic acid (5). Also isolated were 2-oxokolavenic acid (3) and copalic acid (6). Structure elucidation of the compounds was carried out by spectroscopic data interpretation and by the X-ray crystallography of 2 and 4. Three of the new clerodane diterpenes (1, 2, and 5) showed both antifungal activity and inhibition of acetylcholinesterase, and 3 showed a slight inhibition of this enzyme.

Antifungal Agents↗
PubMed2005

Stereoselectivity in the formation of tris-diimine complexes of Fe(II), Ru(II), and Os(II) with a C2-symmetric chiral derivative of 2,2'-bipyridine.

A C2-symmetric enantiopure 4,5-bis(pinene)-2,2'-bipyridine ligand (-)-L was used to investigate the diastereoselectivity in the formation of [ML3]2+ coordination species (M = Fe(II), Ru(II), Os(II), Zn(II), Cd(II), Cu(II), Ni(II)), and [ML2Cl2] (M = Ru(II), Os(II)). The X-ray structures of the [ML3]2+ complexes were determined for Delta-[FeL3](PF6)2, Delta-[RuL3](PF6)2, Lambda-[RuL3](PF6)2, Delta-[OsL3](PF6)2, and Lambda-[OsL3](TfO)2. All of these compounds were also characterized by NMR, CD and UV/VIS absorption spectroscopy. The [FeL3]2+ diastereoisomers were studied in equilibrated solutions at various temperatures and in several solvents. The [RuL3]2+ complexes, which are thermally stable up to 200 degrees C, were photochemically equilibrated.

Journal Article↗
PubMed2005

Synthesis, structure and DNA interaction of cobalt(III) bis-complexes of 1,3-bis(2-pyridylimino)isoindoline and 1,4,7-triazacyclononane.

The complex [CoL(2)](ClO(4)).MeOH (1), where HL is the tridentate 3N ligand 1,3-bis(2-pyridylimino)isoindoline, has been isolated and its X-ray crystal structure successfully determined. It possesses a distorted octahedral structure in which both the ligands are coordinated meridionally to cobalt(III) via one deprotonated isoindoline (L(-)) and two pyridine nitrogen atoms. Interestingly, the average dihedral angle between pyridine and isoindoline rings is 25.9 degrees , indicating that the ligand is twisted upon coordination to cobalt(III). The interaction of the complex with calf-thymus DNA has been studied using various spectral methods and viscosity and electrochemical measurements. For comparison, the DNA interaction of [Co(tacn)(2)]Cl(3) (2), where tacn is facially coordinating 1,4,7-triazacyclononane, has been also studied. The ligand-based electronic spectral band of 1 and the N(sigma)-->Co(III) charge transfer band of 2 exhibit moderate hypochromism with small or no blue shift on interaction with DNA. The intrinsic binding constants calculated reveal that the monopositive complex ion [CoL(2)](+) exhibits a DNA-binding affinity lower than the tripositive complex ion [Co(tacn)(2)](3+). The steric clashes with DNA exterior caused by the second L(-) ligand bound to cobalt(III), apart from the lower overall positive charge on the [CoL(2)](+) complex, dictates its DNA-binding mode to be surface binding rather than partial intercalative interaction expected of the extended aromatic chromophore of deprotonated isoindoline anion. An enhancement in relative viscosity of CT DNA on binding to 1 is consistent with its DNA surface binding. On the other hand, a slight decrease in viscosity of CT DNA was observed on binding to 2 revealing that the smaller cation leads to bending (kinking) and hence shortening of DNA chain length. The electrochemical studies indicate that the DNA-bound complexes are stabilised in the higher Co(III) rather than the lower Co(II) oxidation state, suggesting the importance of electrostatic forces of DNA interaction.

Cobalt↗
PubMed2005

Synthesis and spectroscopic characterization of a new family of Ni(4) spin clusters.

A new family of tetranuclear Ni complexes [Ni(4)(ROH)(4)L(4)] (H(2)L = salicylidene-2-ethanolamine; R = Me (1) or Et (2)) has been synthesized and studied. Complexes 1 and 2 possess a [Ni(4)O(4)] core comprising a distorted cubane arrangement. Magnetic susceptibility and inelastic neutron scattering studies indicate a combination of ferromagnetic and antiferromagnetic pairwise exchange interactions between the four Ni(II) centers, resulting in an S = 4 spin ground state. Magnetization measurements reveal an easy-axis-type magnetic anisotropy with D approximately -0.93 cm(-)(1) for both complexes. Despite the large magnetic anisotropy, no slow relaxation of the magnetization is observed down to 40 mK. To determine the origin of the low-temperature magnetic behavior, the magnetic anisotropy of complex 1 was probed in detail using inelastic neutron scattering and frequency domain magnetic resonance spectroscopy. The spectroscopic studies confirm the easy-axis-type anisotropy and indicate strong transverse interactions. These lead to rapid quantum tunneling of the magnetization, explaining the unexpected absence of slow magnetization relaxation for complex 1.

Journal Article↗
PubMed2005

Helicates of chiragen-type ligands and their aptitude for chiral self-recognition.

Two (-)-5,6-pinene-bipyridine moieties connected by a para-xylylene bridge (so-called chiragen-type ligands), (-)-L1, undergo self-assembly upon reaction with equimolar amounts of CuI to form enantiopure circular hexanuclear P-helicates. If both enantiomers of L1 are used, mixtures of P and M hexanuclear helicates are exclusively obtained through a complete chiral recognition; that is, no mixing of the (+) and (-) ligands, respectively, occurs upon complexation. This was proven by a) NMR spectroscopy where identical spectra to those for complexes with the enantiomerically pure ligands were obtained and b) circular dichroism (CD) spectroscopy. The reaction is completely changed by the use of the corresponding meso-L1. Instead of well-defined species, oligomeric mixtures are observed, a result demonstrating the crucial role played by ligand chirality in self-assembly processes. Structural variations on the chiral ligand L1, such as a meta-xylylene bridge instead of a para-xylylene one (in L4) or four pinene groups instead of two (in L5 and L6), favor nondiscrete coordination assembly.

Journal Article↗
PubMed2005

Packing effects in 4,4'-bis(4-hydroxybutyl)-2,2'-bipyridine and 4,4'-bis(4-bromobutyl)-2,2'-bipyridine.

Structure analyses of 4,4'-bis(4-hydroxybutyl)-2,2'-bipyridine, C18H24N2O2, (I), and 4,4'-bis(4-bromobutyl)-2,2'-bipyridine, C18H22Br2N2, (II), reveal intermolecular hydrogen bonding in both compounds. For (I), O-H...N intermolecular hydrogen bonding leads to the formation of an infinite two-dimensional polymer, and pi stacking interactions are also observed. For (II), C-H...N intermolecular hydrogen bonding leads to the formation of a zigzag polymer. The two compounds crystallize in different crystal systems, but both molecules possess Ci symmetry, with one half molecule in the asymmetric unit.

Journal Article↗