Exploring the Influence of Diamagnetic Ions on the Mechanism of Magnetization Relaxation in {Co<sup>III</sup><sub>2</sub>Ln<sup>III</sup><sub>2</sub>} (Ln = Dy, Tb, Ho) “Butterfly” Complexes

Published on 2017-02-17T15:54:01Z (GMT) by
The synthesis and magnetic and theoretical studies of three isostructural heterometallic [Co<sup>III</sup><sub>2</sub>Ln<sup>III</sup><sub>2</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(<i>o</i>-tol)<sub>4</sub>(mdea)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>] (Ln = Dy (<b>1</b>), Tb (<b>2</b>), Ho (<b>3</b>)) “butterfly” complexes are reported (<i>o</i>-tol = <i>o</i>-toluate, (mdea)<sup>2–</sup> = doubly deprotonated <i>N</i>-methyldiethanolamine). The Co<sup>III</sup> ions are diamagnetic in these complexes. Analysis of the dc magnetic susceptibility measurements reveal antiferromagnetic exchange coupling between the two Ln<sup>III</sup> ions for all three complexes. ac magnetic susceptibility measurements reveal single-molecule magnet (SMM) behavior for complex <b>1</b>, in the absence of an external magnetic field, with an anisotropy barrier <i>U</i><sub>eff</sub> of 81.2 cm<sup>–1</sup>, while complexes <b>2</b> and <b>3</b> exhibit field induced SMM behavior, with a <i>U</i><sub>eff</sub> value of 34.2 cm<sup>–1</sup> for <b>2</b>. The barrier height for <b>3</b> could not be quantified. To understand the experimental observations, we performed DFT and ab initio CASSCF+RASSI-SO calculations to probe the single-ion properties and the nature and magnitude of the Ln<sup>III</sup>–Ln<sup>III</sup> magnetic coupling and to develop an understanding of the role the diamagnetic Co<sup>III</sup> ion plays in the magnetization relaxation. The calculations were able to rationalize the experimental relaxation data for all complexes and strongly suggest that the Co<sup>III</sup> ion is integral to the observation of SMM behavior in these systems. Thus, we explored further the effect that the diamagnetic Co<sup>III</sup> ions have on the magnetization blocking of <b>1</b>. We did this by modeling a dinuclear {Dy<sup>III</sup><sub>2</sub>} complex (<b>1a</b>), with the removal of the diamagnetic ions, and three complexes of the types {K<sup>I</sup><sub>2</sub>Dy<sup>III</sup><sub>2</sub>} (<b>1b</b>), {Zn<sup>II</sup><sub>2</sub>Dy<sup>III</sup><sub>2</sub>} (<b>1c</b>), and {Ti<sup>IV</sup><sub>2</sub>Dy<sup>III</sup><sub>2</sub>} (<b>1d</b>), each containing a different diamagnetic ion. We found that the presence of the diamagnetic ions results in larger negative charges on the bridging hydroxides (<b>1b</b> > <b>1c</b> > <b>1</b> > <b>1d</b>), in comparison to <b>1a</b> (no diamagnetic ion), which reduces quantum tunneling of magnetization effects, allowing for more desirable SMM characteristics. The results indicate very strong dependence of diamagnetic ions in the magnetization blocking and the magnitude of the energy barriers. Here we propose a synthetic strategy to enhance the energy barrier in lanthanide-based SMMs by incorporating s- and d-block diamagnetic ions. The presented strategy is likely to have implications beyond the single-molecule magnets studied here.

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Vignesh, Kuduva R.; Langley, Stuart K.; Murray, Keith S.; Rajaraman, Gopalan (2017): Exploring the Influence of Diamagnetic Ions on the

Mechanism of Magnetization Relaxation in {CoIII2LnIII2} (Ln = Dy, Tb, Ho) “Butterfly”

Complexes. ACS Publications. Collection.