Adding Time-Domain 161Dy Mössbauer to the Mix: a Multitechnique Investigation of Magnetic Transitions in a {CoIII3DyIII3} Cluster with a Toroidal Moment
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The coordination cluster [Co III 3 Dy III 3 (µ 3 -OH) 4 (O 2 C-C 6 H 4 - p -Me) 6 (pmide) 3 (H 2 O) 3 ]Cl 2 ∙10MeCN ( 1 ) (where H 2 pmide = N -2-pyridylmethyldiethanolamine) crystallizes on a threefold site in the trigonal space group P 3 c1 . The cluster core contains one equilateral Dy 3 III triangle and one triangle of diamagnetic Co III ions to give a shuttlecock-like molecular structure. The magnetic spin structure has been investigated using a multi-technique approach. In addition to the magnetic susceptibility, we report 161 Dy Synchrotron Mössbauer Spectroscopy (SMS) which shows an abrupt transition from a non-magnetic to a magnetic state which is in line with the transition observed in complementary measurements. The experimental orientations of the individual axes were independently assessed using torque magnetometry and micro-SQUID measurements and both experiments converged on a spin structure that can be correlated with the crystal structure. The results are also in agreement with those from ab initio CASSCF/SO-RASSI calculations, which also showed that a hydrogen-bonded chloride counterion has a significant effect on the magnetic structure.
