title: Spectroscopic and theoretical study of a mononuclear manganese(III) complex exhibiting a tetragonally compressed geometry.
abstract: Inelastic neutron scattering and high-field electron paramagnetic resonance data are presented for [Mn(bpia)(OAc)(OCH(3))](PF(6)), where bpia is bis(picolyl)(N-methylimidazole-2-yl)amine. Modeling of the data to the conventional fourth-order spin-Hamiltonian yielded the following parameters: D = 3.526(3) cm(-1), E = 0.588(6) cm(-1), B(0)(4) = -0.00084(7) cm(-1), B(2)( 4)= -0.002(2) cm(-1), (4)(4) = -0.0082(5) cm(-1), g(x) = 1.98(1), g(y) = 1.952(6), and g(z) = 1.978(5). The complex is of particular interest given the biochemical activity and the unusual stereochemistry distinguished by a rare example of a tetragonally compressed octahedron and a pronounced angular distortion imposed by the tetradentate tripodal bpia ligand. Ligand field, density functional theory, and complete active space self-consistent field ab initio calculations are presented that aim to relate the spectroscopic data to the molecular geometry.
authors: Laboratory for Neutron Scattering, ETH Zürich and Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland.
authors: Quirin
authors: Q
authors: Scheifele
authors: Christoph
authors: C
authors: Riplinger
authors: Frank
authors: F
authors: Neese
authors: Høgni
authors: H
authors: Weihe
authors: Anne-Laure
authors: AL
authors: Barra
authors: Fanni
authors: F
authors: Juranyi
authors: Andrei
authors: A
authors: Podlesnyak
authors: Philip L W
authors: PL
authors: Tregenna-Piggott