Comparing Electrical Magnetochiral Anisotropy and Chirality-Induced Spin Selectivity.

The combination of chirality and magnetism has steadily grown over the past decennia into an area of intense research that evolves around two distinct manifestations and in two nonoverlapping communities: electrical magnetochiral anisotropy (eMChA) and chirality-induced spin-selectivity (CISS). Here, we discuss the similarities and differences of these two effects. Whereas the original CISS reports suggest an intimate relation with eMChA, magnetoresistance (MR) results on two-terminal chiral devices attributed to CISS have symmetry properties that are different from those of eMChA. At the same time, the magnitudes of CISS MR and eMChA turn out to be similar when normalized to current density and spin polarization, suggesting a common underlying mechanism.

Two successive single crystal phase transitions involving the coordination sphere of antimony in PhSb(dmit), the first organo-antimony(III) dithiolene complex.

PhSb(dmit) (dmit(2)(-), 4,5-dithiolato-1,3-dithiole-2-thione), the first neutral organo-antimony dithiolene complex, has been synthesized by addition of PhSbCl(2) on a suspension of Na(2)(dmit). The complex was characterized by spectroscopic ((1)H and (13)C NMR and IR) methods and elemental analysis. Its crystal structure was determined by X-ray diffraction at room temperature in the monoclinic P2(1)/c space group, with a = 12.580(3), b = 8.9756(18), c = 15.905(3) A, beta = 109.06(3) degrees, V = 1697.5(6) A(3), Z = 4. A coordinating THF molecule was found in the structure and the coordination geometry around the antimony atom is of distorted pseudopentagonal bipyramid type, if taking into account the Sb.O and secondary Sb.S interactions, as well as the stereochemically active 5s(2) lone pair. The intermolecular Sb.S and S.S contacts, shorter than the sum of van der Waals radii of corresponding atoms, lead to the formation of a three-dimensional polymeric network in the solid state. A second X-ray diffraction experiment, performed at 85 K, revealed a very similar monoclinic unit cell with the noncentrosymmetrical space group P2(1) with a = 12.613(3), b = 8.9876(18), c = 15.109(3) A, beta = 107.01(3) degrees, V = 1637.8(6), Z = 4. The structural differences with the first one are basically due to the rotation of the THF ligand in the coordination sphere of the antimony center, leading to the loss of every inversion center found at room temperature. A temperature variable X-ray diffraction study on a PhSb(dmit) single-crystal allowed the detection, with a remarkable accuracy, of two successive first-order phase transitions, the first occurring at T = 162.5 K, while the second was observed at T = 182.5 K. Subsequently, a third set of X-ray data was collected at 180 K and the resulting structure (monoclinic, P2(1)/c, a = 16.736(3), b = 8.9653(18), c = 33.132(7) A, beta = 91.98(3) degrees, V = 4968.2(17), Z = 12) derives from the two others by a common b axis, a 3-fold cell volume increase, and the presence of only one-third of the inversion centers present at room temperature. A DSC analysis, showing two endothermic peaks at the expected temperatures, confirms the occurrence of the two structural phase transitions, also in agreement with preliminary Raman data.

Gold(I) and Gold(0) Complexes of Phosphinine-Based Macrocycles.

A "CO-like matrix", showing coordination analogous to that of carbonyl groups, is provided by silacalix[4]phosphinine macrocycles. Reaction with Au(I) leads to the first gold(I) complexes of macrocycles, which can be reduced with sodium or potassium to the paramagnetic gold(0) complexes (an example is shown), as evidenced by cyclic voltammetry and EPR spectroscopy.

Silacalix-

The synthesis of polyphosphinine macrocycles, which consist of a 16-membered ring with four phosphorus atoms (P4) and a 12-membered ring with three phosphorus atoms (P3), is described. Their high coordination ability is demonstrated by the quantitative synthesis of the rhodium and iridium cation complexes of the P4 macrocycle and by quantitative synthesis of the W(CO)3 complex of the P3 compound. Unlike the other available macrocyclic ligands bearing oxygen, sulfur, di- or tricoordinate nitrogen, and even tricoordinate phosphorus as ligating atoms, which are all essentially final sigma donors, these dicoordinate phosphorus-based macrocycles have strong pi-acceptor properties. Their use can be envisaged for the stabilization of negative oxidation states of transition metals or in reductive catalysis.