Synthesis, characterization and magnetic properties of one-dimensional 4,4′-bipyridine-bridged manganese(II) complex: Crystal structure of [Mn(μ-4,4′-bipy)(4,4′-bipy)(NCS)2(H2O)2]n

Preparation of New Ligand‐Deficient Thiocyanato Compounds with Cooperative Magnetic Phenomena by Thermal Decomposition of Their Ligand‐Rich Precursors

“…Similar thermal behavior was also reported for the ligand-rich 1:2 analogues 1-Mn [7,8] and 1-Co, [9] but none of their intermediates were structurally characterized and investigated for their magnetic properties. In the course of systematic investigations on magnetostructural correlations we prepared the analogous ligand-rich 1:2 hydrates 1-Mn, 1-Co, and 1-Ni to obtain their ligand-deficient intermediates by thermal decomposition.…”

“…Similar thermal behavior is also found for its analogues 1-Mn and 1-Co, comparable with that found in the literature (Figure S17, Supporting Information). [8,9] On the basis of the experimental mass losses, it can be assumed that in the first heating step the solvent-free 1:2 compounds of composition [M(NCS) 2 (bipy) 2 ] n with M = Mn (2-Mn), Co (2-Co), and Ni (2-Ni) and in the second step the ligand-deficient 1:1 compounds of composition [M(NCS) 2 (bipy)] n with M = Mn (3-Mn), Co , and Ni (3-Ni) are formed. On further heating, the remaining ligands are emitted, leading to the formation of M(NCS) 2 , which decompose on further heating.…”

“…The ligand-rich 1:2 hydrate [{Ni(NCS) 2 (bipy)(H 2 O) 2 }· (bipy)] n (1-Ni) is isotypic to its analogues 1-Mn, [7,8] 1-Fe, [11] and 1-Co [9] and crystallizes in the centrosymmetric triclinic space group P1 with one formula unit in the unit cell (Table 8). The crystal structure was refined by the Rietveld method with the structure model of its analogue 1-Co as the starting structure model.…”

“…However, these results are in accordance with that found in the literature. [8] In all compounds the metal centers are separated by eight atoms of the bipy ligand, and therefore, no significant magnetic exchange interactions mediated by this ligand can be expected. Thus, cooperative magnetic phenomena can only be observed in those compounds for which the metal centers are bridged by the thiocyanato anions, which is the case in the ligand-deficient 1:1 intermediates 3-Mn, 3-Co, and 3-Ni and for literature known 1:1 compound 3-Cu.…”

New Cu(II) complexes with polydentate chelating Schiff base ligands: Synthesis, structures, characterisations and biochemical activity studies

“…Several criteria have been developed for ascertaining the bonding mode of thiocyanate ligands [21]. A ν(C-N) frequency below 2100 cm −1 is characteristic of both N-bonded thiocyanate ligand and free thiocyanate ion [22]. Bands at 2082, 781, 472 cm −1 for 1 and 2090, 2075, 785, 476 cm −1 for 2 correspond to ν(C-N), ν(C-S) and ν(N-C-S), respectively, consistent with terminally nitrogen-bound NCS − groups [22].…”