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How strongly are the magnetic anisotropy and coordination numbers correlated in lanthanide based molecular magnets?

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Abstract

Ab initio CASSCF + RASSI-SO investigations on a series of lanthanide complexes [LnIII = Dy(1), Tb(2), Ce(3), Nd(4), Pr(5) and Sm(6)] have been undertaken and in selected cases (for 1, 2, 3 and 4) coordination number (C.N.) around the LnIII ion has been gradually varied to ascertain the effect of C.N. on the magnetic anisotropy. Our calculations reveal that complex 3 possesses the highest barrier height for reorientation of magnetisation (Ueff) and predict that 3 is likely to exhibit Single Molecule Magnet (SMM) behaviour. Complex 5 on the other hand is predicted to preclude any SMM behaviour as there is no intrinsic barrier for reorientation of magnetization. Ground state anisotropy of all the complexes show mixed behaviour ranging from pure Ising type to fully rhombic behaviour. Coordination number around the lanthanide ion is found to alter the magnetic behaviour of all the lanthanide complexes studied and this is contrary to the general belief that the lanthanide ions are inert and exert small ligand field interaction. High symmetric low-coordinate LnIII complexes are found to yield large Ueff values and thus should be the natural targets for achieving very large blocking temperatures.

TOC content: We have undertaken detailed ab-initio studies on {LnIII(NO3)6}3- [LnIII=Dy(1),Tb(2),Ce(3),Nd(4),Pr(5) and Sm(6)] complexes to gain insight into the effective barrier height for relaxation of magnetization and mechanism underlying this barrier. Additionally, we have also probed the effect of co-ordination number on magnetic anisotropy in these complexes.

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Acknowledgements

GR would like to acknowledge financial support from the Government of India through the Department of Science and Technology (SR/S1/IC-41/2010; SR/NM/NS-1119/2011) and Indian Institute of Technology, Bombay to access the high performance computing facility. TG would like to thank UGC New Delhi for JRF fellowship.

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

    TULIKA GUPTA & GOPALAN RAJARAMAN

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  1. TULIKA GUPTA
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Correspondence to GOPALAN RAJARAMAN.

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GUPTA, T., RAJARAMAN, G. How strongly are the magnetic anisotropy and coordination numbers correlated in lanthanide based molecular magnets?. J Chem Sci 126, 1569–1579 (2014). https://doi.org/10.1007/s12039-014-0691-z

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