title: New type of single chain magnet: pseudo-one-dimensional chain of high-spin Co(II) exhibiting ferromagnetic intrachain interactions.
abstract: Two new six-coordinated high-spin Co(II) complexes have been synthesized through the reactions of Co(II) salts with dipyridylamine (dpamH) and 5-nitro-salicylaldehyde (5-NO2-saloH) or 3-methoxy-salicylaldehyde (3-OCH3-saloH) under argon atmosphere: [Co(dpamH)2(5-NO2-salo)]NO3 (1) and [Co(dpamH)2(3-OCH3-salo)]NO3·1.3 EtOH·0.4H2O (2). According to the crystal packing of compound 1, two coordination cations are linked with two nitrate anions into a cyclic dimeric arrangement via N-H···O and C-H···O hydrogen bonds. In turn, these dimers are assembled into (100) layers through π-π stacking interactions between inversion-center related pyridine rings of the dpamH ligands. The crystal packing of compound 2 reveals a 1D assembly consisting solely from the coordination cations, which is formed by π-π stacking interactions between pyridine rings of one of the dpamH along the [010] and another 1D assembly of the coordination cations and nitrate anions through the N-H···O hydrogen-bonding interactions along the [001] direction. All complexes were magnetically characterized, and a new approximation method was used to fit the magnetic susceptibility data in the whole temperature range 2-300 K on the basis of an empirical expression which allows the treatment of each cobalt(II) ion in axial symmetry as an effective spin S(eff) = 1/2. In zero-field, dynamic magnetic susceptibility measurements show slow magnetic relaxation below 5.5 K for compound 2. The slow dynamics may originate from the motion of broad domain walls and is characterized by an Arrhenius law with a single energy barrier Δr/k(B) = 55(1) K for the [10-1488 Hz] frequency range. In order to reveal the importance of the crystal packing in the SCM behavior, a gentle heating process to 180 °C was carried out to remove the solvent molecules. The system, after heating, undergoes a major but not complete collapse of the network retaining to a small percentage its SCM character.
authors.affiliation: Department of Chemistry, Laboratory of Inorganic Chemistry, Aristotle University, Thessaloniki 54 124, Greece. vtagkoul@chem.auth.gr
authors.forename: V
authors.initials: V
authors.lastname: Tangoulis
authors.forename: M
authors.initials: M
authors.lastname: Lalia-Kantouri
authors.forename: M
authors.initials: M
authors.lastname: Gdaniec
authors.forename: Ch
authors.initials: Ch
authors.lastname: Papadopoulos
authors.forename: V
authors.initials: V
authors.lastname: Miletic
authors.forename: A
authors.initials: A
authors.lastname: Czapik
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D059346:Magnets; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D003035:Cobalt