Anion coordination directed synthesis patterns for [Ni₄] aggregates: structural changes for thiocyanate coordination and ligand arm hydrolysis

Abstract

Competitive bridging modes of HO− and NCS− were explored for four NiII-based coordination aggregates in cubane and dicubane topology.

А New Series of Schiff Base Ni(II)4 Cubanes: Evaluation of Magnetic Coupling Via Carboxylate Bridges

“…Comparison with isotropic exchange parameters (Table 1) determined from the experimental data shows that DFT calculations overestimates this type of the exchange. It is well-known that the isotropic exchange in Ni 4 cubane is dependent on Ni-O-Ni angle, [3][4][5]52] and also in this series of compounds 1-3, the magneto-structural linear correlation can be established -Fig. 4.…”

“…In general, the Ni 4 O 4 cubane may exhibit either ferromagnetic or antiferromagnetic interactions among the nickel ions, depending upon the combination of the cubane topology and Ni-O-Ni angles. The structure of the cubane cores can be modified by introducing alterations in the coordinating ligands and the change in crystallization conditions such as solvent, temperature, guest molecules and pH [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. This is apparently helpful for the synthesis of new molecular magnets allowing preparation of the Co(II) or Ni(II) cubanes with the dominant ferromagnetic interactions among the metal centers and non-negligible magnetic anisotropy of the ground state.…”

“…This is apparently helpful for the synthesis of new molecular magnets allowing preparation of the Co(II) or Ni(II) cubanes with the dominant ferromagnetic interactions among the metal centers and non-negligible magnetic anisotropy of the ground state. Such compounds can exhibit slow relaxation of magnetization of molecular origin characteristic for Single-Molecule Magnets (SMMs) [3][4][5][6].…”

“…A great number of the cubane structures based on Schiff bases are formed on the basis of derivatives of salicylic aldehyde [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Such complexes are widely investigated due to the simplicity of their synthesis.…”

A high-nuclearity complex containing a decanuclear iron(iii)/oxo cage in a football-like structure and rare (R-/S)-hemiacetalate ligands in a butterfly-like format

“…[1][2][3][4][5][6] There are numerous reasons for the interest in the synthesis and study of high nuclearity 3d molecular metal clusters at moderate-to-high oxidation states. 7,8 High nuclearity 3d metal clusters, 9,10 especially the ones that include Ni II , Co II , Mn III and Fe III , oen display fascinating structures, occasionally attractive properties, [11][12][13][14] including single molecular magnet (SMM) and coupled SMM behavior, [15][16][17] and promising applications for data storage, quantum computing and spintronics. 18,19 The high nuclearity iron(III)-oxo chemistry has being developed over many years by virtue of their important role in bioinorganic chemistry, molecular magnetism and so on.…”