Synthesis of heptanuclear Ni4Dy3 coordination aggregate using tridentate ligand: X-ray structure, magnetism and theoretical studies

Bhanja, A., Smythe, L., Kotrle, K., Ortu, F., Herchel, R., Murrie, M. and Ray, D. (2021) Synthesis of heptanuclear Ni4Dy3 coordination aggregate using tridentate ligand: X-ray structure, magnetism and theoretical studies. Inorganica Chimica Acta, 526, 120524. (doi: 10.1016/j.ica.2021.120524)

Abstract

The Schiff base ligand, 2-(((2-hydroxybenzyl)imino)methyl)phenol (H2L) having ONO donor centres are utilized to synthesize {Ni4Dy3} coordination aggregate following the support of six benzoate bridging groups. Sequential addition of Dy(NO3)3·6H2O and NiCl2·6H2O to H2L followed by PhCO2Na completes the coordination driven aggregation of heptanuclear Na[Ni4Dy3(L)4(μ3-OH)4(μ1,1,3,3-PhCO2)2(μ1,3-PhCO2)4(CH3OH)4]∙CH2Cl2·9H2O (1) having 2,3,6M7 − 1 topology. Two adjacent perpendicular inverse Ni2Dy2 partial di-cubane units sharing a common vertex through the central DyIII ion resulted a new structural arrangement within the Ni − Dy family of coordination aggregates. The complex shows no slow magnetic relaxation under zero applied fields and only shows a very weak field dependent magnetization. The DFT calculations revealed weak ferromagnetic exchange between benzoato-bridged NiII ions, whereas the CASSCF calculations were used to identify magnetic anisotropy in NiII and DyIII ions resulting in low-lying excited states of DyIII ions with significant probability for the quantum tunneling of the magnetization, which rationalize the observed fast dynamics in the magnetic properties.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Smythe, Ms Lucy and Murrie, Professor Mark
• Authors: Bhanja, A., Smythe, L., Kotrle, K., Ortu, F., Herchel, R., Murrie, M., and Ray, D.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Inorganica Chimica Acta
• Publisher: Elsevier
• ISSN: 0020-1693
• ISSN (Online): 1873-3255
• Published Online: 12 July 2021