Search results for "Supramolecular"
showing 10 items of 830 documents
A Hydrogen-Bonded Supramolecular meso-Helix
2003
[EN] A new one-dimensional hydrogen-bonded polymer with a unique meso-helical structure has been prepared from the spontaneous self-assembly in the solid-state of meta-substituted phenylene dioxamic acid diethyl ester monomers. The helical nature of this molecule and its self-complementary character, through intermolecular hydrogen bonding between oxamic acid ester functions, are the two main factors responsible for the crystalline aggregation process, as confirmed by both experimental X-ray crystallographic data and theoretical ab initio calculations.
Binding Mode and Selectivity of a Scorpiand-Like Polyamine Ligand to Single- and Double-Stranded DNA and RNA: Metal- and pH-Driven Modulation
2017
The interaction of a polyazacyclophane ligand having an ethylamine pendant arm functionalized with an anthryl group (L), with the single-stranded polynucleotides polyA, polyG, polyU, and polyC as well as with the double-stranded polynucleotides polyA-polyU, poly(dAT)(2), and poly(dGC)(2) has been followed by UV/Vis titration, steady state fluorescence spectroscopy, and thermal denaturation measurements. In the case of the single-stranded polynucleotides, the UV/Vis and fluorescence titrations permit to distinguish between sequences containing purine and pyrimidine bases. For the double-stranded polynucleotides the UV/Vis measurements show for all of them hypochromicity and bathochromic shif…
Nanoporosity, Inclusion Chemistry, and Spin Crossover in Orthogonally Interlocked Two-Dimensional Metal-Organic Frameworks
2015
[Fe(tvp)(2)(NCS)(2)] (1) (tvp=trans-(4,4-vinylenedipyridine)) consists of two independent perpendicular stacks of mutually interpenetrated two-dimensional grids. This uncommon supramolecular conformation defines square-sectional nanochannels (diagonal approximate to 2.2nm) in which inclusion molecules are located. The guest-loaded framework 1@guest displays complete thermal spin-crossover (SCO) behavior with the characteristic temperature T-1/2 dependent on the guest molecule, whereas the guest-free species 1 is paramagnetic whatever the temperature. For the benzene-guest derivatives, the characteristic SCO temperature T-1/2 decreases as the Hammet sigma(p) parameter increases. In general, …
Six-coordinate CoIII and four-coordinate MII (M = Co, Zn) mixed-valence dimers supported by a deprotonated pyridine amide ligand: magnetism of a CoII…
2009
Using a pyridine amide ligand 4-methyl-2-{N-(2-pyridyl)carbamoyl}pyridine (HL), in its deprotonated form, binuclear mixed-valence homonuclear bimetallic complexes [CoIII,II2(L)3(X)]X·S [X = Cl (1); X = Br, S = CH3OH (2)] and heteronuclear bimetallic complex [CoIIIZnII(L)3(Cl)]Cl·CH3OH·5H2O (3) have been synthesized. Structural analysis revealed that trivalent cobalt is in distorted octahedral and bivalent cobalt/zinc is in distorted tetrahedral environment. Three L(−) ligands provide six-coordination by utilizing three pyridine amide units (pyridine N and amide N donor set) in a facial mode, which in turn places three 4-methylpyridine nitrogens to coordinate to another metal center, which c…
Metallophilicity-assisted assembly of phosphine-based cage molecules.
2014
A family of supramolecular cage molecules has been obtained via self-assembly of the phosphine-gold coordination complexes following an aurophilicity-driven aggregation approach. Use of the di- (PP) or tridentate (PPP) phosphine ligands Pn (n = 2, 3) with rigid polyaromatic backbones leads to clean formation of the coordination Pn(Au(tht))n(n+) species, sequential treatment of which with H2O/NEt3 and excess of H2NBu(t) gives the finite 3D structures of two major types. The cylindrical-like hexametallic cages [(PPAu2)3(μ3-NBu(t))2](2+) are based on the diphosphines PP = 1,4-bis(diphenylphosphino)benzene (1), 4,4'-bis(diphenylphosphino)biphenyl (2), 4,4"-bis(diphenylphosphino)terphenyl (3), w…
Two complexes of Pt(IV) and Au(III) with 2,2'-dipyridylamine and 2,2'-dipyridylaminide ligands
2014
Two noble metal complexes involving ancillary chloride ligands and chelating 2,2′-bipyridylamine (Hdpa) or its deprotonated derivative (dpa), namely [bis(pyridin-2-yl-κN)amine]tetrachloridoplatinum(IV), [PtCl4(C10H9N3)], and [bis(pyridin-2-yl-κN)aminido]dichloridogold(III), [AuCl2(C10H8N3)], are presented and structurally characterized. The metal atom in the former has a slightly distorted octahedral coordination environment, formed by four chloride ligands and two pyridyl N atoms of Hdpa, while the metal atom in the latter has a slightly distorted square-planar coordination environment, formed by two chloride ligands and two pyridyl N atoms of dpa. The difference in conjugation between the…
Structural analysis and magnetic properties of the copper(II) dicyanamide complexes [Cu2(dmphen)2(dca)4], [Cu(dmphen)(dca)(NO3)] and [Cu(4,4′-dmbpy)(…
2004
Abstract The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu2(dmphen)2(dca)4] (1), [Cu(dmphen)(dca)(NO3)]n (2) and [Cu(4,4′-dmbpy)(H2O)(dca)2] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4′-dmbpy=4,4′-dimethyl-2,2′-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen…
Self-Assembled One- and Two-Dimensional Networks Based on NH2Me2[ReX5(DMF)] (X = Cl and Br) Species: Polymorphism and Supramolecular Isomerism in Re(…
2011
Three mononuclear rhenium(IV) compounds of general formula NH 2 Me 2 [ReX 5 (DMF)] [NH 2 Me 2 + = dimethylammonium cation, DMF = N,N-dimethylformamide, and X = Cl (1 and 2) and Br (3)] have been prepared and characterized. In all three cases, the rhenium atom is six-coordinated by five chloro (1 and 2) or bromo (3) atoms and one oxygen atom from a DMF molecule (1―3) building a somewhat distorted octahedral surrounding. Short Re IV ―X · · · X―Re IV contacts and H-bonds occur in the crystal lattice generating novel supramolecular Re(IV) architectures. 1 and 2 are polymorphs and supramolecular isomers that exhibit supramolecular ladder-like ( 1 ) and rectangular two-dimensional grids (2), the …
Two new supramolecular architectures of singly phenoxo-bridged copper(II) and doubly phenoxo-bridged manganese(II) complexes derived from an unusual …
2009
International audience; Two new coordination complexes {[(L)Cu2('-L)(NO3)(CH3OH)0.3(H2O)0.7]·NO3}[Cu(L)(NO3)(CH3OH)] (1) and [Mn2(-L)2(H2O)(1-N3)2(CH3OH)] (2) derived from (E)-N-(2-hydroxy-3-methoxybenzylidene)acetohydrazide [LH] have been synthesized. The new potentially tetradentate ONOO donor hydrazone ligand [LH] has shown considerable metal ion selective phenoxo bridging in 1 and 2. It has coordinated copper(II) ions in its tridentate as well as in tetradentate fashion whereas for manganese(II) ions it solely showed its tetradentate character. In 1 the two adjacent pentacoordinate copper(II) centers are connected by a rare single phenoxo linkage of the hydrazone ligand whereas 2 is a d…
An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior.
2018
By employing the subcomponent self-assembly approach utilizing 5,10,15,20-tetrakis(4-aminophenyl)porphyrin or its zinc(II) complex, 1H-4-imidazolecarbaldehyde, and either zinc(II) or iron(II) salts, we were able to prepare O-symmetric cages having a confined volume of ca. 1300 Å3 . The use of iron(II) salts yielded coordination cages in the high-spin state at room temperature, manifesting spin-crossover in solution at low temperatures, whereas corresponding zinc(II) salts led to the corresponding diamagnetic analogues. The new cages were characterized by synchrotron X-ray crystallography, high-resolution mass spectrometry, and NMR, Mössbauer, IR, and UV/Vis spectroscopy. The cage structures…