Field‐Induced SMM Behaviour of Tetranuclear Coordination Clusters with a Cubane [Ni4O4] Core

• Published in: European journal of inorganic chemistry Vol. 26; no. 2
• Main Authors: Sarkar, Arijit, Basu, Debayan, Gómez‐García, Carlos J., Nayek, Hari Pada
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 10.01.2023; Wiley Subscription Services, Inc
• Subjects: [Ni4O4] cubane core; Anisotropy; Chemical analysis; Chemistry; Chemistry, Inorganic & Nuclear; Clusters; Coordination cluster; Cubane; Dimethylformamide; Ferromagnetism; Imines; Infrared spectroscopy; Inorganic chemistry; Magnetic properties; Magnets; Physical Sciences; Science & Technology; Single crystals; Single-molecule magnet; X-ray Diffraction; Single-molecule magnet; X-ray Diffraction; NUCLEARITY; LIGANDS; POLYOXOTUNGSTATE; [Ni4O4] cubane core Coordination cluster; NI(II) COMPLEXES; Magnetic properties
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202200565

Two tetranuclear Ni(II) complexes: [Ni4(HL1)4] ⋅ H2O (1) and [Ni4(HL2)4] ⋅ 1.5 dmf (2) where dmf=dimethylformamide, H3L1=4‐(tert‐butyl)‐2‐(((2‐hydroxy‐5‐nitrophenyl)imino)methyl)‐6‐(hydroxymethyl)phenol and H3L2=4‐(tert‐butyl)‐2‐(hydroxymethyl)‐6‐(((2‐hydroxyphenyl)‐imino)methyl)phenol, have been prepared and characterized by single crystal X‐Ray diffraction, elemental analysis and FT‐IR spectroscopy. The solid‐state structures reveal the formation of highly symmetric and asymmetric [Ni4O4] cubane cores in complexes 1 and 2, respectively. Extensive magnetic studies show that both complexes present ferromagnetic exchange interactions between the Ni(II) ions within the cubane core with g=2.113(3), J1=−7.89(8) cm−1, J2=13.3(1) cm−1 and |D|=11.3(4) cm−1 (for 1) and g=2.206(4), J1=1.0(1) cm−1, J2=7.8(1) cm−1 and |D|=8.7(2) cm−1 (for 2). The large anisotropy, high ground spin state (arising from the ferromagnetic coupling) and the good isolation of the clusters provided by the Schiff base ligands, give rise to the first examples of field‐induced single‐molecule magnets (FI−SMM) in Ni4O4 clusters and to the highest energy barrier reported to date in a Ni4O4 cluster. Two new tetranuclear coordination cluster containing a symmetric or an asymmetric [Ni4O4] cubane core have been synthesized. Both clusters exhibited field‐induced single‐molecule magnet (FI−SMM) behaviour.