Tetrairon(III) single-molecule magnets [Fe4 (pPy)2 (dpm)6 ] (1) (H3 pPy=2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol, Hdpm=dipivaloylmethane) have been deliberately organized into supramolecular chains by reaction with Ru(II) Ru(II) or Ru(II) Ru(III) paddlewheel complexes. The products [Fe4 (pPy)2 (dpm)6 ][Ru2 (OAc)4 ](BF4 )x with x=0 (2 a) or x=1 (2 b) differ in the electron count on the paramagnetic diruthenium bridges and display hysteresis loops of substantially different shape. Owing to their large easy-plane anisotropy, the s=1 diruthenium(II,II) units in 2 a act as effective seff =0 spins and lead to negligible intrachain communication. By contrast, the mixed-valent bridges (s=3/2, seff =1/2) in 2 b introduce a significant exchange bias, with concomitant enhancement of the remnant magnetization. Our results suggest the possibility to use electron transfer to tune intermolecular communication in redox-responsive arrays of SMMs.

Redox-Controlled Exchange Bias in a Supramolecular Chain of Fe4 Single-Molecule Magnets / Nava, Andrea; Rigamonti, Luca; Zangrando, Ennio; Sessoli, Roberta; Wernsdorfer, Wolfgang; Cornia, Andrea. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - ELETTRONICO. - 54:30(2015), pp. 8777-8782. [10.1002/anie.201500897]

Redox-Controlled Exchange Bias in a Supramolecular Chain of Fe4 Single-Molecule Magnets

NAVA, ANDREA;RIGAMONTI, Luca;CORNIA, Andrea
2015

Abstract

Tetrairon(III) single-molecule magnets [Fe4 (pPy)2 (dpm)6 ] (1) (H3 pPy=2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol, Hdpm=dipivaloylmethane) have been deliberately organized into supramolecular chains by reaction with Ru(II) Ru(II) or Ru(II) Ru(III) paddlewheel complexes. The products [Fe4 (pPy)2 (dpm)6 ][Ru2 (OAc)4 ](BF4 )x with x=0 (2 a) or x=1 (2 b) differ in the electron count on the paramagnetic diruthenium bridges and display hysteresis loops of substantially different shape. Owing to their large easy-plane anisotropy, the s=1 diruthenium(II,II) units in 2 a act as effective seff =0 spins and lead to negligible intrachain communication. By contrast, the mixed-valent bridges (s=3/2, seff =1/2) in 2 b introduce a significant exchange bias, with concomitant enhancement of the remnant magnetization. Our results suggest the possibility to use electron transfer to tune intermolecular communication in redox-responsive arrays of SMMs.
11-giu-2015
54
30
8777
8782
Redox-Controlled Exchange Bias in a Supramolecular Chain of Fe4 Single-Molecule Magnets / Nava, Andrea; Rigamonti, Luca; Zangrando, Ennio; Sessoli, Roberta; Wernsdorfer, Wolfgang; Cornia, Andrea. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - ELETTRONICO. - 54:30(2015), pp. 8777-8782. [10.1002/anie.201500897]
Nava, Andrea; Rigamonti, Luca; Zangrando, Ennio; Sessoli, Roberta; Wernsdorfer, Wolfgang; Cornia, Andrea
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