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Role of Lanthanide-Ligand bonding in the magnetization relaxation of mononuclear single-ion magnets: A case study on Pyrazole and Carbene ligated LnIII(Ln=Tb, Dy, Ho, Er) complexes

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Abstract

Ab initio CASSCF + RASSI-SO + SINGLE_ANISO and DFT based NBO and QTAIM investigations were carried out on a series of trigonal prismatic M(BcMe)3 (M = Tb(1), Dy(2), Ho(3), Er(4), [BcMe]−= dihydrobis(methylimidazolyl)borate) and M(BpMe)3 (M = Tb(1a), Dy(2a), Ho(3a), Er(4a) [BpMe]−= dihydrobis(methypyrazolyl)borate) complexes to ascertain the anisotropic variations of these two ligand field environments and the influence of Lanthanide-ligand bonding on the magnetic anisotropy. Among all the complexes studied, only 1 and 2 show large Ucal (computed energy barrier for magnetization reorientation) values of 256.4 and 268.5 cm−1, respectively and this is in accordance with experiment. Experimentally only frequency dependent χ” tails are observed for complex 1a and our calculation predicts a large Ucalof 229.4 cm−1 for this molecule. Besides these, none of the complexes (3, 4, 2a, 3a and 4a) computed to possess large energy barrier and this is affirmed by the experiments. These observed differences in the magnetic properties are correlated to the Ln-Ligand bonding. Our calculations transpire comparatively improved Single-Ion Magnet (SIM) behaviour for carbene analogues due to the more axially compressed trigonal prismatic ligand environment. Furthermore, our detailed Mulliken charge, spin density, NBO and Wiberg bond analysis implied stronger Ln...H–BH agostic interaction for pyrazole analogues. Further, QTAIM analysis reveals the physical nature of coordination, covalent, and fine details of the agostic interactions in all the eight complexes studied. Quite interestingly, for the first time, using the Laplacian density, we are able to quantify the prolate and oblate nature of the electron clouds in lanthanides and this is expected to have a far reaching outcome beyond the examples studied.

Calculations were carried out on a series on Ln(BcMe)3 and Ln(BpMe)3 (Ln = Tb, Dy, Ho, Er) complexes to ascertain the anisotropic variations of two ligand field environments and the influence of Lanthanide-ligand bonding on the magnetic anisotropy. Using the Laplacian density, we are able to quantify the prolate and oblate nature of the electron clouds in lanthanides.

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Acknowledgements

GR would like to thank SERB (EMR/2014/00024) for the funding. TG would like to thank UGC New Delhi for SRF fellowship. GV would like to thank Indian Institute of Technology Bombay for Post-Doctoral fellowship.

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  1. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400 076, India

    TULIKA GUPTA, GUNASEKARAN VELMURUGAN, THAYALAN RAJESHKUMAR & GOPALAN RAJARAMAN

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  1. TULIKA GUPTA
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Supplementary Information (SI)

We have summarised the energies (cm−1), corresponding g-tensors, tunnel splitting (cm−1), crystal field parameters and angle between main magnetic axis of ground state energy multiplet and higher excited levels of all the Kramers doublets and pseudo-doublets in 2, 2a, 4, 4a and 1, 1a, 3, 3a, respectively, in Tables S1–S9. The orientation of the principal anisotropy axis (gz) for complexes a) 2 and b) 2a are given in Figure S1. The core structural moieties of complexes atom numbers correspond to the representation of Mulliken charges are given in the Figure S2. The second-order perturbation theory computed donor-acceptor charge transfer stabilisation energy in all the eight complexes are given in Figures S3–S18. The molecular graphs of the complexes and the contour line diagram of the Laplacian of electron density drawn along the three carbon (C-C-C) plane are given in the Figures S19 and S20 respectively.

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GUPTA, T., VELMURUGAN, G., RAJESHKUMAR, T. et al. Role of Lanthanide-Ligand bonding in the magnetization relaxation of mononuclear single-ion magnets: A case study on Pyrazole and Carbene ligated LnIII(Ln=Tb, Dy, Ho, Er) complexes. J Chem Sci 128, 1615–1630 (2016). https://doi.org/10.1007/s12039-016-1147-4

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