Search results for "Nuclear magnetic resonance"

Reversible Dimerization of Tetraureas Derived from Calix[4]Arenes

1999

Calix[4]arene derivatives, substituted at the wider rim by four urea functions are easily available in great variety. In apolar solvents like benzene or chloroform they dimerize via NH…O=C hydrogen bonds encapsulating a single solvent molecule as guest. The exclusive formation of dimers has been proved in solution by NMR, while their shape has been characterized by single crystal X-ray analysis. The kinetic stability and the rate of the guest exchange have been studied by NOESY experiments using a derivative with lower symmetry.

Unravelling the fine structure of stacked bipyridine diamine-derived C-3-discotics as determined by X-ray diffraction, quantum-chemical calculations,…

2011

An in depth investigation of the fine structure adopted by the helical stacks of C3-discotics 1 incorporating three 3,3'-diamino-2,2'-bipyridine units is described. In the bulk the molecules display liquid crystalline behaviour in a temperature window of >300 K and an ordered rectangular columnar mesophase (Colro) with an inter-disc distance of 3.4 Å is assigned. X-Ray diffraction on aligned samples has also revealed a helical superstructure in the liquid crystalline state, and a rotation angle of 13–16° between consecutive discs. The proposed superstructure in the bulk phase has been further substantiated by a combination of quantum-chemical calculations and solid-state NMR spectroscopy…

Competitive gold-activation modes in terminal alkynes: an experimental and mechanistic study.

2013

The competition between π- and dual σ,π-gold-activation modes is revealed in the gold(I)-catalyzed heterocyclization of 1-(o-ethynylaryl)urea. A noticeable effect of various ligands in gold complexes on the choice of these activation modes is described. The cationic [Au(IPr)](+) (IPr=2,6-bis(diisopropylphenyl)imidazol-2-ylidene) complex cleanly promotes the π activation of terminal alkynes, whereas [Au(PtBu3 )](+) favors intermediate σ,π species. In this experimental and mechanistic study, which includes kinetic and cross-over experiments, several σ-gold, σ,π-gold, and other gold polynuclear reaction intermediates have been isolated and identified by NMR spectroscopy, X-ray diffraction, or …

Solid state NMR studies of gels derived from low molecular mass gelators

2016

The emergence of NMR crystallography provides a unique opportunity to study solids, gels and xerogels, thereby providing ample information to elucidate molecular packing in the native gel. This review details the importance as well as the application of solid state NMR spectroscopy combined with other analytical tools to study gels derived from low molecular mass organo- and hydrogelators.

Ni participation in the magnetism of Fe-Ni-Si-B amorphous alloys.

1987

$^{61}\mathrm{Ni}$ M\"ossbauer measurements at 4.2 K have been performed on (${\mathrm{Fe}}_{\mathrm{x}}$${\mathrm{Ni}}_{1\mathrm{\ensuremath{-}}\mathrm{x}}$${)}_{77}$${\mathrm{Si}}_{1013}$ amorphous alloys with x=0.0, 0.1, and 0.9. Ni atoms in ${\mathrm{Ni}}_{77}$${\mathrm{Si}}_{10}$${\mathrm{B}}_{13}$ bear no magnetic moment, whereas in (${\mathrm{Fe}}_{0.1}$${\mathrm{Ni}}_{0.9}$${)}_{77}$${\mathrm{Si}}_{10}$${\mathrm{B}}_{13}$ and (${\mathrm{Fe}}_{0.9}$${\mathrm{Ni}}_{0.1}$${)}_{77}$${\mathrm{Si}}_{10}$${\mathrm{B}}_{13}$ their moments are, respectively 0.38${\ensuremath{\mu}}_{B}$ and 0.65${\ensuremath{\mu}}_{B}$. Our results, together with the literature data, show that Ni atoms in Fe-…

Magnetic alignment of aliphatic lamellae

1993

Abstract Magnetic alignment of mesophases is normally only considered possible when the molecule contains an aromatic ring system. In this paper we report on the mesomorphous behaviour of a polyalkylacrylate resin with average sidechain length 22 and the alignment of its lamellae in cast films by annealing in a strong magnetic field.

1986

The molecular order and mobility of two liquid-crystalline polyacrylates with phenyl benzoate moieties as mesogenic side groups and (CH2)m spacers (m = 2 and m = 6) were investigated by pulsed 2H NMR. The mesogenic side groups were isotopically labelled at the terminal phenylene ring. In the glassy state the orientational distribution function was characterized from the angular dependence of the 2H NMR line shape of samples macroscopically ordered in their nematic phase by the 8,4 T magnetic field of an NMR spectrometer. It was found to be Gaussian with widths of ± 18,5° and ± 10,5° for the m = 2 frozen nematic and m = 6 frozen smectic system, respectively. The phenylene rings undergo 180° …

1H NMR study of dynamical inequivalence of cations in [C(NH2)3]3Sb2Cl9

2001

Abstract The proton NMR second moment and spin–lattice relaxation time have been studied for polycrystalline tris-guanidinium nonachlorodiantimonate(III) in a wide temperature range. The C 3 reorientation of two types of the cations, hindered by very different potential barriers (20.5 and 54.5 kJ/mol) has been revealed. An unusually large dynamical inequivalence of two cations evidently reflects their different crystalline environments.

Coexistence of spin-crossover and antiferromagnetic coupling phenomena in the novel dinuclear Fe(II) complex [Fe(dpa)(NCS)2]2bpym

2003

Abstract The iron(II) spin crossover dinuclear compound [Fe(dpa)(NCS) 2 ] 2 bpym where dpa = 2,2 ′ -dipyridylamine and bpym = 2,2 ′ -bipyrimidine has been synthesized and characterized. Variable-temperature magnetic susceptibility and 57 Fe Mossbauer spectroscopy data provide evidence for a rather complete and continuous S=2 ( HS )↔S=0 (LS) spin-crossover behavior taking place in the temperature range 400–50 K (T 1/2 =245 K ) without the presence of a plateau at 50% of conversion. The absence of such plateau, which is characteristic of all dinuclear compounds so far studied, is interpreted in terms of synergetic effect between intramolecular and intermolecular interactions.

Optical absorption of magnesia-supported gold clusters and nanoscale catalysts: Effects due to the support, clusters, and adsorbants

2005

Polarization-resolved optical spectra of magnesia-supported gold clusters ${\mathrm{Au}}_{N}∕\mathrm{Mg}\mathrm{O}$ $(N=1,2,4,8)$, bound at a surface color center ${F}_{s}$ of the MgO(100) face, are calculated from the time-dependent density functional theory. The optical lines for $N=1,2$ are dominated by transitions that involve strong hybridization between gold and ${F}_{s}$ states whereas for $N=4,8$ intracluster transitions dominate. The theoretical optical spectra are sensitive to cluster structure and adsorbants (here CO and ${\mathrm{O}}_{2}$ molecules on ${\mathrm{Au}}_{8}∕{F}_{s}@\mathrm{Mg}\mathrm{O}$) which suggests polarization-resolved optical spectroscopy as a powerful tool t…