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Single‐Molecule‐Magnet Behavior in the Family of [Ln(OETAP) 2 ] Double‐Decker Complexes (Ln=Lanthanide, OETAP=Octa(ethyl)tetraazaporphyrin)
Author(s) -
GiménezAgulló Nelson,
de Pipaón Cristina Sáenz,
Adriaenssens Louis,
Filibian Marta,
MartínezBelmonte Marta,
EscuderoAdán Eduardo C.,
Carretta Pietro,
Ballester Pablo,
GalánMascarós José Ramón
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402869
Subject(s) - lanthanide , crystallography , square antiprism , chemistry , molecule , phthalocyanine , sublimation (psychology) , single molecule magnet , magnetization , stereochemistry , organic chemistry , physics , ion , psychology , quantum mechanics , magnetic field , psychotherapist
Double‐decker complexes of lanthanide cations can be readily prepared with tetraazaporphyrins (porphyrazines). We have synthesized and characterized a series of neutral double‐decker complexes [Ln(OETAP) 2 ] (Ln=Tb 3+ , Dy 3+ , Gd 3+ , Y 3+ ; OETAP=octa(ethyl)tetraazaporphyrin). Some of these complexes show analogous magnetic features to their phthalocyanine (P c ) counterparts. The Tb 3+ and Dy 3+ derivatives exhibit single‐molecule magnet (SMM) behavior with high blocking temperatures over 50 and 10 K, respectively. These results confirm that, in double‐decker complexes that involve Tb or Dy, the (N 4 ) 2 square antiprism coordination mode has an important role in inducing very large activation energies for magnetization reversal. In contrast with their P c counterparts, the use of tetraazaporphyrin ligands endows the presented [Ln(OETAP) 2 ] complexes with extraordinary chemical versatility. The double‐decker complexes that exhibit SMM behavior are highly soluble in common organic solvents, and easily processable even through sublimation.