Single‐Molecule‐Magnet Behavior in the Family of [Ln(OETAP)2] Double‐Decker Complexes (Ln=Lanthanide,OETAP=Octa(ethyl)tetraazaporphyrin) |
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Authors: | Nelson Giménez‐Agulló Dr Cristina Sáenz de?Pipaón Louis Adriaenssens Dr Marta Filibian Marta Martínez‐Belmonte Eduardo C Escudero‐Adán Prof Pietro Carretta Prof Pablo Ballester Prof José Ramón Galán‐Mascarós |
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Institution: | 1. Institute of Chemical Research of Catalonia (ICIQ), Av. Pa?sos Catalans, 16, 43007, Tarragona (Spain), Fax: (+34)?977‐920‐224;2. Department of Physics “A. Volta”, University of Pavia‐CNISM, Via Bassi 6, 27100 PaVia2 (Italy), Fax: (+39)?0382‐987‐478;3. Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluis Companys, 23, 08010, Barcelona (Spain) |
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Abstract: | 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=Tb3+, Dy3+, Gd3+, Y3+; OETAP=octa(ethyl)tetraazaporphyrin). Some of these complexes show analogous magnetic features to their phthalocyanine (Pc) counterparts. The Tb3+ and Dy3+ 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 (N4)2 square antiprism coordination mode has an important role in inducing very large activation energies for magnetization reversal. In contrast with their Pc 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. |
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Keywords: | lanthanides magnetic properties NMR spectroscopy porphyrinoids sandwich complexes |
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