Realista S, Fitzpatrick A J, Santos G, Ferreira L P, Barroso S, Pereira L C J, Bandeira N A G, Neugebauer P, Hrubý J, Morgan G G, van Slageren J, Calhorda M J, Martinho P N
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal.
School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland.
Dalton Trans. 2016 Aug 2;45(31):12301-7. doi: 10.1039/c6dt02538b.
Single ion magnet behaviour is reported for a mononuclear Mn(iii) ion with tridentate Schiff-base ligands which exhibits a tetragonal Jahn-Teller elongation along the Namine-Mn-Namine axis and crystallises with two crystallographically distinct Mn(iii) cations (unit A and unit B). While magnetic measurements show a large and negative axial zero-field splitting (D = -4.73 cm(-1)), HF-EPR reveal two distinct large axial Ds (D = -4.60 cm(-1) for unit A and D = -4.18 cm(-1) for unit B), thus resulting in the largest D known to date for a Mn(iii) single ion magnet. AC magnetic measurements at 2000 Oe allowed determination of the energy barrier for spin reversal (10.19 K) and spin reversal relaxation time (1.476 × 10(-6) s) for the Mn(iii) ion. Computational studies were used to characterise the electronic structure and substantiate the zero field splitting in the Mn(iii) complex.
