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Dalton Trans. 2016 Aug 2;45(31):12301-7. doi: 10.1039/c6dt02538b.

A Mn(iii) single ion magnet with tridentate Schiff-base ligands.

Author information

1
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal. pnmartinho@ciencias.ulisboa.pt.
2
School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland.
3
BioISI, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal and Department of Physics, University of Coimbra, 3004-516 Coimbra, Portugal.
4
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal.
5
C2TN, Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional 10, ao Km 139, 7, 2695-066 Bobadela LRS, Portugal.
6
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal. pnmartinho@ciencias.ulisboa.pt and Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal and Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans, 16-43007 Tarragona, Spain.
7
Institut für Physikalische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.

Abstract

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.

PMID:
27440193
DOI:
10.1039/c6dt02538b

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