Search results for " Geometry"
showing 10 items of 2294 documents
A coarse-graining procedure for polymer melts applied to 1,4-polybutadiene
2009
We present a coarse-graining procedure for homopolymer melts mapping intra- as well as inter-molecular interactions from a chemically realistic united atom description to a bead-spring type molecular model. On the coarse-grained level the repeat units interact through bond-length and bond angle potentials and a non-bonded Lennard-Jones type interaction. The latter one is of the 7,4 form and softer than the typically employed 12,6 interactions. The coarse-graining of the intramolecular interactions follows well developed procedures, however, we point out in which way the non-bonded intramolecular interactions in the chemically realistic model should be treated. The parameters of the non-bond…
Mean square radius of gyration and hydrodynamic radius of jointed star (dumbbell) and H-comb polymers
1996
Equations for the mean square radius of gyration and the hydrodynamic radius for jointed stars (dumbbells) and H-combs are derived, based on random flight statistics for each subchain. Comparision with literature data on computer simulations and experimental data for H-combs show good agreement for the g-value of the mean square radius of gyration even in good solvents. This suggests that for the mean square radius of gyration the relative dimension of a H-comb relative to the linear molecule of the same degree of polymerization is not altered significantly by long range interactions, as in the case of star polymers. For the hydrodynamic radius the situation is different. Fair agreement is …
Coordination Geometry Preference Regulates the Structure and Dynamics of Metallo-Supramolecular Polymer Networks
2021
Metal–ligand interactions are extensively used for the development of biomimetic polymers. Macroscopic properties of such systems are closely tied to the microscopic structure and dynamics of not o...
Near Isotropic D4d Spin Qubits as Nodes of a Gd(III)-Based Metal-Organic Framework
2021
Embedding coherent spin motifs in reproducible molecular building blocks is a promising pathway for the realization of quantum technologies. Three-dimensional (3D) MOFs are a versatile platform for the rational design of extended structures employing coordination chemistry. Here, we report the synthesis and characterization of a gadolinium(III)-based MOF, [Gd(bipyNO)4](TfO)3·xMeOH (bipyNO = bipyridine,N,N′-dioxide; TfO = triflate; and MeOH = methanol) (quMOF-1), which presents a unique coordination geometry that leads to a tiny magnetic anisotropy (in terms of D, an equivalent zero-field splitting would be achieved by D = 0.006 cm–1) even compared with regular Gd(III) complexes. Pulsed elec…
A novel Cu(II) dimer containing oxime-hydrazone Schiff base ligands with an unusual mode of coordination: Study of magnetic, autoreduction and soluti…
2013
Abstract Synthesis of a new hydrazone based Schiff base ligand, 3-methylpyrazole-5-carbohydrazone of 2,3-butanedione monoxime (HL) is reported. The reaction of Cu(ClO4)2·6H2O with HL in any ratio in ethanol affords the dinuclear complex [CuL(EtOH)]2(ClO4)2·2H2O (1). An unusual coordination mode of the ligand was observed, in which the ligand forms stable six and five membered chelate rings around the metal centres without enolization of the carbonyl group of the hydrazone moiety. The same coordination behavior of the ligand was observed in its cobalt(III) complex. The reaction of CoCl2·6H2O in methanol with the ligand HL affords the mononuclear complex [CoL2]Cl (2). Both 1 and 2 were charac…
Structural study of NaNdGa4S8, a luminescent material with low-concentration quenching
1988
Abstract Single-crystal X-ray diffraction analysis and optical investigations of NaNdGa 4 S 8 show that Nd 3+ ions are essentially distributed in two of the three square antiprismatic sites of a CaGa 2 S 4 -type lattice. The NdS 8 polyhedra are isolated (minimum NdNd distance: 6.07 A) so the interactions responsible for concentration quenching of the luminescence are considerably reduced
The First Examples of a Crown Ether Intramolecularly Encapsulating Mono- and Diorganotin Dications: Synthesis and Structures of [PhSnCH2([16]crown-5)…
2010
The reaction of silver perchlorate with [PhI 2 SnCH 2 ([16]crown-5)] (1) and [I 3 SnCH 2 ([16]crown-5)] (2) gave the organotin(IV)-substituted crown ether complexes [PhSnCH 2 ([16]crown-5)][ClO 4 ] 2 (3) and [HOSnCH 2 ([16]crown-5)][Y] 2 (4: Y= ClO 4 , 5: Y=CF3 S 03 ) , respectively. All compounds have been isolated as air-stable materials and characterised by 1 H, 13 C, 119 Sn and 119 Sn MAS (5) NMR spectroscopy, ESIMS spectrometry, elemental analysis and by single-crystal X-ray diffraction analysis. The molecular structures of 3-5 show that the tin(IV) cation fits perfectly into the crown ether cavity and is coordinated by the five oxygen atoms of the ring to give a pentagonal bipyramidal…
Cyclometallation reactions in complexes of the type Rh(oq)(CO)[P(o-BrC6F4)Ph2]. The molecular structure of F4)Ph2] (oq = 8-hydroxyquinolinate)
1984
Cyclometallation occurs when a solution of the complex Rh(oq)(CO)(PCBr), (PCBr = 2-bromo-3,4,5,6-tetrafluorophenyldiphenylphosphine; oq = 8-hydroxyquinolinate) in toluene is refluxed, giving Rh(oq)2(PC) (PC = P(C6F4)(C6H5)2) and a dimeric compound, not yet completely characterized, formulated as Rh2Br(oq)(PCBr)2. Rh(oq)2(PC) was characterized by elemental analysis, by conductance measurements, and by 19F, 31P NMR and infrared spectroscopy. Its molecular structure was determined by single-crystal X-ray methods and refined by standard procedures to final agreement factors R and Rw of 0.067 and 0.060 for 5346 observed data. Lattice constants are 15.8494(6), 14.7188(5), 14.6675(5) A and β 96.93…
Crystal and molecular structure of the tris(1,10-phenanthroline)potassium salt of μ-hydridobis[pentacarbonylchromium(0)]
1984
Abstract The crystal and molecular structure of [K(phen)3][Cr2(CO)10(μ-H)] has been determined by X-ray diffraction. The compound crystallizes in the space group P 1 with a 11.884(4), b 13.968(4), c 15.612(6) A, α 112.6(1), β 99.7(1) and γ 106.2(1)° and Z = 2. The structure was refined to R = 0.066 and RW = 0.067 for 3692 counter data with I ⩾ 3σ(I). The complex anion [Cr2(CO)10(μ-H)] adopts a bent Cr-H-Cr configuration with the equatorial carbonyl groups of the two independent Cr(CO)5 moieties in an eclipsed configuration. The Cr⋯Cr distance is 3.394(3) A and the two CrH bonds are 1.74(7) and 1.71(7) A. The CrHCr bond angle is 159(3)°. In the dimeric complex cation [K(phen)3]2, located …
Copper(ii) and Zn(ii) coordination chemistry of tetraaza[n]cyclophanes
2003
The acid–base behaviour and Zn2+ and Cu2+ metal coordination chemistry of the novel orthocyclophane ligands 2,5,8,11-tetraaza[12]orthocyclophane (L2) and 2,5,9,12-tetraaza[13]orthocyclophane (L3) and metacyclophane 2,5,8,11-tetraaza[12]metacylophane (L1) are studied. Important differences in the chemistry of these compounds are found depending on the substitution of the aromatic ring. The ortho derivatives are much more basic in their first two protonation steps while the metacyclophane presents much larger constants in the third and fourth protonation stages. The crystal structure of the picrate salt of [H2L3]2+ shows an alternate disposition of the protons in the molecule with formation o…