Complete NMR assignment of 3, 4‐seco‐lup‐20(29)‐en‐3‐oic acid from Decatropis bicolor

Complete ¹H and ¹³C NMR chemical shift assignments for 3,4‐seco‐lup‐20(29)‐en‐3‐oic acid ( 1 ) have been established by means of two‐dimensional COSY, HSQC, HMBC and NOESY spectroscopic experiments as well as by analysis of MS data. Compound 1 was isolated from Decatropis bicolor (Zucc.) Radlk. (Rutaceae) in addition to six coumarins and one alkaloid of known structure. Copyright © 2012 John Wiley & Sons, Ltd.     

Commensurate-incommensurate magnetic phase transition in magnetoelectric single crystal LiNiPO(4)

Neutron scattering studies of single crystal LiNiPO4 reveal a spontaneous first-order commensurate-incommensurate magnetic phase transition. Short- and long-range incommensurate phases are intermediate between the high temperature paramagnetic and the low temperature antiferromagnetic phases. The modulated structure has a predominant antiferromagnetic component, giving rise to satellite peaks in the vicinity of the fundamental antiferromagnetic Bragg reflection, and a ferromagnetic component, giving rise to peaks at small momentum transfers around the origin at (0,+/-Q,0). The wavelength of the modulated magnetic structure varies continuously with temperature. It is argued that the incommensurate short- and long-range phases are due to spin-dimensionality crossover from a continuous to the discrete Ising state.     

Subphthalocyanines: tuneable molecular scaffolds for intramolecular electron and energy transfer processes

A series of four subphthalocyanine-C(60) fullerene dyads have been prepared through axial functionalization of the macrocycle with m-hydroxybenzaldehyde and a subsequent dipolar cycloaddition reaction. The subphthalocyanine moiety has been peripherally functionalized with substituents of different electronic character, namely fluorine or iodine atoms and ether or amino groups, thus reaching a control over its electron-donating properties. This is evidenced in cyclic voltammetry experiments by a progressive shift to lower potentials, by ca. 200 mV, of the first oxidation event of the SubPc unit in the dyads. As a consequence, the energy level of the SubPc(*)(+)-C(60)(*)(-) charge-transfer state may be tuned so as to compete with energy transfer deactivation pathways upon selective excitation of the SubPc component. For instance, excitation of those systems where the level of the radical pair lies high in energy triggers a sequence of exergonic photophysical events that comprise (i) nearly quantitative singlet-singlet energy transfer to the C(60) moiety, (ii) fullerene intersystem crossing, and (iii) triplet-triplet energy transfer back to the SubPc. On the contrary, the stabilization of the SubPc(*)(+)-C(60)(*)(-) radical pair state by increasing the polarity of the medium or by lowering the donor-acceptor redox gap causes charge transfer to dominate. In the case of 1c in benzonitrile, the thus formed radical pair has a lifetime of 0.65 ns and decays via the energetically lower lying triplet excited state. Further stabilization is achieved for dyad 1d, whose charge-transfer state would lie now below both triplets. The radical pair lifetime consequently increases in more than 2 orders of magnitude with respect to 1c and presents a significant stabilization in less polar solvents, revealing a low reorganization energy for this kind of SubPc-C(60) systems.     

Half-quadratic cost functions for phase unwrapping

We present a generic regularized formulation, based on robust half-quadratic regularization, for unwrapping noisy and discontinuous wrapped phase maps. Two cases are presented: the convex case and the nonconvex case. The unwrapped phase with the convex formulation is unique and robust to noise; however, the convex function solution deteriorates as a result of real discontinuities in phase maps. Therefore we also present a nonconvex formulation that, with a parameter continuation strategy, shows superior performance.     

Reductive electrochemistry of spiromethanofullerenes

The synthesis and electrochemical properties of spiromethanofullerenes 1-6 are described. The syntheses were achieved via the diazomethane route, and the regioisomeric distribution of bis-adducts 3 was determined by (1)H NMR, UV-vis, and HPLC analysis. The electrochemistry of these compounds in dichloromethane exhibits, besides several reversible reductions, some irreversible waves. Reductive electrolysis of 1 and 3-5 in dichloromethane leads to the removal of the addend and thus to the formation of C60. Reductive electrolysis of 1, 2 and 6 in dichloromethane leads to a different reaction, which we tentatively assign to a reaction with the solvent to form fullerene-CH2Cl products. Electrolyses in the less reactive solvent THF lead to adduct removal for 1 and 3-5. Interestingly, significant formation of bis-adducts from the corresponding monoadducts was observed for 4 and 5. These electrochemically induced reactions, namely addend removal, reaction with the solvent, and addend transfer are influenced by the structure of the addend and by the choice of solvent.     

Origin of constant loss in ionic conductors

We have analyzed the constant loss contribution to the ac conductivity in the frequency range 10 Hz-1 MHz and temperatures down to 8 K, for two Li ionic conductors, one crystalline (Li(0.18)La(0.61)TiO(3)) and the other glassy (61SiO(2);35Li(2)O.3Al(2)O3.P(2)O(5)). As temperature is increased a crossover is observed from a nearly constant loss to a fractional power law frequency dependence of the ac conductivity. At any fixed frequency omega, this crossover occurs at a temperature T such that omega approximately nu(0)exp(-E(m)/k(B)T), where nu(0) is the attempt frequency and E(m) is identified with the barrier for Li+ ions to leave their wells.