title: Role of Magnetic Exchange Interactions in the Magnetization Relaxation of {3d-4f} Single-Molecule Magnets: A Theoretical Perspective.
abstract: Combined density functional and ab initio calculations are performed on two isomorphous tetranuclear {Ni3 (III) Ln(III) } star-type complexes [Ln=Gd (1), Dy (2)] to shed light on the mechanism of magnetic exchange in 1 and the origin of the slow magnetization relaxation in complex 2. DFT calculations correctly reproduce the sign and magnitude of the J values compared to the experiments for complex 1. Acute ∢Ni-O-Gd bond angles present in 1 instigate a significant interaction between the 4fxyz orbital of the Gd(III) ion and 3d${{_{x{^{2}}- y{^{2}}}}}$ orbital of the Ni(II) ions, leading to rare and strong antiferromagnetic Ni⋅⋅⋅Gd interactions. Calculations reveal the presence of a strong next-nearest-neighbour Ni⋅⋅⋅Ni antiferromagnetic interaction in complex 1 leading to spin frustration behavior. CASSCF+RASSI-SO calculations performed on complex 2 suggest that the octahedral environment around the Dy(III) ion is neither strong enough to stabilize the mJ |±15/2〉 as the ground state nor able to achieve a large ground-state-first-excited-state gap. The ground-state Kramers doublet for the Dy(III) ion is found to be the mJ |±13/2〉 state with a significant transverse anisotropy, leading to very strong quantum tunneling of magnetization (QTM). Using the POLY_ANISO program, we have extracted the JNiDy interaction as -1.45 cm(-1) . The strong Ni⋅⋅⋅Dy and next-nearest-neighbour Ni⋅⋅⋅Ni interactions are found to quench the QTM to a certain extent, resulting in zero-field SMM behavior for complex 2. The absence of any ac signals at zero field for the structurally similar [Dy(AlMe4 )3 ] highlights the importance of both the Ni⋅⋅⋅Dy and the Ni⋅⋅⋅Ni interactions in the magnetization relaxation of complex 2. To the best of our knowledge, this is the first time that the roles of both the Ni⋅⋅⋅Dy and Ni⋅⋅⋅Ni interactions in magnetization relaxation of a {3d-4f} molecular magnet have been established.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076 (India).
authors.forename: Saurabh Kumar
authors.initials: SK
authors.lastname: Singh
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076 (India).
authors.forename: Mohammad Faizan
authors.initials: MF
authors.lastname: Beg
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076 (India). rajaraman@chem.iitb.ac.in.
authors.forename: Gopalan
authors.initials: G
authors.lastname: Rajaraman
keywords: CASSCF calculations; ab initio calculations; density functional calculations; magnetic properties; {3d-4f} SMMs; {Ni-Ln} SMMs; {Ni3-Ln} complexes