title: A spin-frustrated trinuclear copper complex based on triaminoguanidine with an energetically well-separated degenerate ground state.
abstract: We present the synthesis and crystal structure of the trinuclear copper complex [Cu3(saltag)(bpy)3]ClO4·3DMF [H5saltag = tris(2-hydroxybenzylidene)triaminoguanidine; bpy = 2,2'-bipyridine]. The complex crystallizes in the trigonal space group R3̅, with all copper ions being crystallographically equivalent. Analysis of the temperature dependence of the magnetic susceptibility shows that the triaminoguanidine ligand mediates very strong antiferromagnetic interactions (JCuCu = -324 cm(-1)). Detailed analysis of the magnetic susceptibility and magnetization data as well as X-band electron spin resonance spectra, all recorded on both powdered samples and single crystals, show indications of neither antisymmetric exchange nor symmetry lowering, thus indicating only a very small splitting of the degenerate S = (1)/2 ground state. These findings are corroborated by density functional theory calculations, which explain both the strong isotropic and negligible antisymmetric exchange interactions.
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: Eike T
authors: ET
authors: Spielberg
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: Aksana
authors: A
authors: Gilb
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: Daniel
authors: D
authors: Plaul
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: Daniel
authors: D
authors: Geibig
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: David
authors: D
authors: Hornig
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: Dirk
authors: D
authors: Schuch
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: Axel
authors: A
authors: Buchholz
authors: ‡Centre for Advanced Spin Resonance, Clarendon Laboratory, University of Oxford, OX1 3PU Oxford, United Kingdom.
authors: Arzhang
authors: A
authors: Ardavan
authors: †Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07743 Jena, Germany.
authors: Winfried
authors: W
authors: Plass