From Paramagnetic to Single‐Molecule Magnet Behaviour in Heterobimetallic Compounds Containing the Tetrakis(thiocyanato‐κN)cobaltate(II) Anion

• Published in: European journal of inorganic chemistry 2018-02, Vol.2018 (6), p.816-825
• Main Authors: Kalinke, Lucas H. G., Cardoso, Jocielle C. O., Rabelo, Renato, Valdo, Ana K., Martins, Felipe T., Cano, Joan, Julve, Miguel, Lloret, Francesc, Cangussu, Danielle
• Format: Article
• Language: English
• Subjects: Anions; Cobalt; Diamagnetism; Energy gap; Inorganic chemistry; Magnetic induction; Magnetic permeability; Magnetic properties; Magnetic relaxation; Nickel; Nickel compounds; Single‐ion magnets; Structure elucidation
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201701177

Four heterobimetallic compounds of formula [Ni(Me6trans[14]dieneN4)][Co(NCS)4] (1 and 2), [Ni(Me6trans[14]dieneN4)]2[Co(NCS)4](ClO4)2·H2O (3) and [Ni(Me6trans[14]dieneN4)]2[Co(NCS)4](PF6)2 (4) (Me6trans[14]dieneN4 = 5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradeca‐4,11‐diene) have been synthesised and structurally characterised. Their structures are formed of square‐planar [Ni(Me6trans[14]dieneN4)]2+ cations and tetrahedral [Co(NCS)4]2– anions. The variable‐temperature magnetic properties of 2–4 mainly obey the zero‐field splitting effects (D) of the 4A2 ground‐state term of the pseudo‐tetrahedral [Co(NCS)4]2– anionic complex (2D is the energy gap between the |±1/2> and |±3/2> levels of the spin quadruplet when E = 0), the square‐planar nickel(II) unit being diamagnetic. Analysis of their magnetic data through the spin Hamiltonian H = D[Sz2 – S(S + 1)/3] + E(Sx2 – Sy2) + gβHS led to the following best‐fit parameters: g = 2.216(17), D = +3.74(12) cm–1 and E/D = 0.0137(6) for 2, g = 2.335(20), D = +11.6(4) cm–1 and E/D = 0.002(4) for 3 and g = 2.298(15), D = +7.29(17) cm–1 and E/D = 0.068(3) for 4. The Q‐band EPR spectra of powdered samples of 2–4 in the temperature range 4.0–20 K support the positive signs of D. With an applied dc field, the ac susceptibility data for 3 and 4 below 4.5 K reveal a slow magnetic relaxation, which is a characteristic of single‐ion magnet (SIM) behaviour. Slow relaxation of the magnetisation has been observed in compounds containing the [Co(NCS)4]2– complex anion, the geometry of which strongly deviates from ideal Td.