Synthetic diversity and change in nuclearity in [Co–Dy] coordination aggregates: bridge removal, solvent induced structural reorganization and AC susceptibility measurements
Dipmalya Basak, Jan van Leusen, Tulika Gupta, Paul Kögerler, Debashis Ray
Abstract
Three new cobalt(ii/iii)-dysprosium(iii) complexes, [DyIII3CoII2CoIII2(L1)2(O2CCMe3)8(OH)4(OMe)2(H2O)4]·Dy(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2·4H2O (1), [DyIII3CoII2CoIII2(L2)2(O2CCMe3)8(OH)4(OMe)2(MeOH)2(H2O)2]·Dy(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2·4MeOH (2) and DyIII2CoII2CoIII2(L2)2(O2CCMe3)10(OH)2 (3) have been reported. In the heptanuclear 3d-4f monocationic aggregates in 1 and 2 the three dysprosium and four cobalt sites are arranged into a vertex shared dicubane structure, induced by two structure-directing ligands. Interestingly, a unique and previously unknown dysprosium(iii)-pivalate based counter anion, Dy(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2-, was trapped by the monocationic cores during crystallization. MeCN induced structural rearrangement of 2 through loss of OMe- bridges and dysprosium(iii) ions at the shared vertex resulted in the hexanuclear 3d-4f neutral aggregate 3, in which two dysprosium and four cobalt sites exhibit a near planar disposition. HRMS(+ve) of solutions of 1 and 2 revealed the pathway for aggregation processes and solvent induced structural transformation along with the importance of bridging OMe- in directing the formation of these compounds. Magnetic studies show a non-zero out-of-phase component in the AC susceptibility measurements of 1 but not in 2 and 3, although 1 and 2 have a very similar {CoIII2CoII2DyIII3} core and another DyIII center. Ab initio single-ion calculations point to the different single-ion anisotropic behavior for DyIII centers (energy in cm-1 and g-tensors) as well as negative and positive D values for CoII sites in 1 and 2 respectively reaffirming the experimental result. However, calculations envision that, zero-field out-of-phase signal and no out-of-phase signal in 1 and 2 respectively do not solely generate from the single-ion Dy/Co anisotropies and the overall relaxation mechanism can be understood by considering the exchange interactions between DyIII-DyIII and DyIII-CoII centres.