A New Class of Lanthanide Complexes with Three Ligand Centered Radicals: NMR Evaluation of Ligand Field Energy Splitting and Magnetic Coupling

Combination of three radical anionic Ph-BIAN ligands (Ph-BIAN=bis-(phenylimino)-acenaphthenequinone) with lanthanoid ions leads to a series of homoleptic, six-coordinate complexes of the type Ln(Ph-BIAN)₃. Magnetic coupling data were measured by paramagnetic solution NMR spectroscopy. Combining ¹H NMR with ²H NMR of partially deuterated compounds allowed a detailed study of the magnetic susceptibility anisotropies over a large temperature range. The observed chemical shifts were separated into ligand- and metal-centered contributions by comparison with the Y analogue (diamagnetic at the metal). The metal-centered contributions of the complexes with the paramagnetic ions could then be separated into pseudocontact and Fermi contact shifts. The latter is large within the Ph-BIAN scaffold, which shows that magnetic coupling is significant between the lanthanide ion and the radical ligand. Pseudocontact shifts were further correlated to structural data obtained from X-ray diffraction experiments. Ligand-field parameters were determined by fitting the temperature dependence of the observed magnetic susceptibility anisotropies. The electronic structure determined by this approach shows, that the Er and Tm analogues are candidates for single molecule magnets (SMM). These results demonstrate the possibilities for the application of NMR spectroscopy in investigations of paramagnetic systems in general and single molecule magnets in particular.     

Phenomenological studies on B~0 → [K~-π~+]_(S/V)[π~+π~-]_(V/S) → K~-π~+π~+π~- decay

Within the quasi-two-body decay model,we study the localized CP violation and branching fraction of the four-body decay B~0→[K~-π~+]_(s/V)[π~+π~-]_(V/)S→K-π~+π~-π~+ when the K~-π~+and π~-π~+ pair invariant masses are0.35 m(K~-π~+)2.04 GeV and 0 mπ~-π~+1.06 GeV,with the pairs being dominated by the K_0~*(700)~0,K~*(892)~0,K~*(1410)~0,K_0~*(1430) and K~*(1680)~0,and fo(500),ρ~0(770),ω(782) and fo(980) resonances,respectively.When dealing with the dynamical functions of these resonances,fo(500),ρ~0(770),fo(980) and K_0~*(1430) are modeled with the Bugg model,Gounaris-Sakurai function,Flatte formalism and LASS lineshape,respectively,while the others are described by the relativistic Breit-Wigner function.Adopting the end point divergence parameters ρA ∈[0,0.5] andΦ_A∈[0,2π],our predicted results are F_(CP)(B~0→K~-π~+π~+π~-)∈[-0.365,0.447] and B(B~0→K-π~+π~+π~-)∈[6.11,185.32] x 10~(-8),based on the hypothetical qq structures for the scalar mesons in the QCD factorization approach.Meanwhile,we calculate the CP violating asymmetries and branching fractions of the two-body decays B~0→SV(VS) and all the individual four-body decays B~0→SV(VS)→K~-π~+π~-π~+,respectively.Our theoretical results for the two-body decays B~0→K~*(892)~0 fo(980),B~0→K_0~*(1430)~0ω(782),B~0→K~*(892)~0 f~0(980),B~0→K_0~*(1430)~0ρ,and B~0→(1430)~0ω are consistent with the available experimental data,with the remaining predictions await testing in future high precision experiments.