Enneanuclear [Ni6Ln3] cages: [LnIII3] triangles capping [NiII6] trigonal prisms including a [Ni6Dy3] single-molecule magnet

Canaj, A. B. , Tzimopoulos, D. I., Siczek, M., Lis, T., Inglis, R. and Milios, C. J. (2015) Enneanuclear [Ni6Ln3] cages: [LnIII3] triangles capping [NiII6] trigonal prisms including a [Ni6Dy3] single-molecule magnet. Inorganic Chemistry, 54(14), pp. 7089-7095. (doi: 10.1021/acs.inorgchem.5b01149)

Abstract

The use of (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) ligand, H3L, in Ni/Ln chemistry has led to the isolation of three new isostructural [NiII6LnIII3] metallic cages. More specifically, the reaction of Ni(ClO4)2·6H2O, the corresponding lanthanide nitrate salt, and H3L in MeCN, under solvothermal conditions in the presence of NEt3, led to the isolation of three complexes with the formulas [Ni6Gd3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (1·5.75MeCN·2Et2O·1.5H2O), [Ni6Dy3(OH)6(HL)6(NO3)3]·2MeCN·2.7Et2O·2.4H2O (2·2MeCN·2.7Et2O·2.4H2O), and [Ni6Er3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (3·5.75MeCN·2Et2O·1.5H2O). The structure of all three clusters describes a [LnIII3] triangle capping a [NiII6] trigonal prism. Direct current magnetic susceptibility studies in the 5–300 K range for complexes 1–3 reveal the different nature of the magnetic interactions within the clusters: dominant antiferromagnetic exchange interactions for the DyIII and ErIII analogues and dominant ferromagnetic interactions for the GdIII example. Alternating current magnetic susceptibility measurements under zero external dc field displayed fully formed temperature- and frequency-dependent out-of-phase peaks for the [NiII6DyIII3] analogue, establishing its single molecule magnetism behavior with Ueff = 24 K.

• Item Type: Articles
• Additional Information: This research has been cofinanced by the European Union (European Social Fund, ESF) and Greek national funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF) via the THALES Programme (C.J.M. and A.B.C.). R.I. would like to thank The Royal Society of Edinburgh for funding. D.I.T. would like to thank the 89439/2012 Grant of the Aristotle University of Thessaloniki.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Tsanai, Dr Angelos
• Authors: Canaj, A. B., Tzimopoulos, D. I., Siczek, M., Lis, T., Inglis, R., and Milios, C. J.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Inorganic Chemistry
• Publisher: American Chemical Society
• ISSN: 0020-1669
• ISSN (Online): 1520-510X