Tunable magnetic anisotropy in luminescent cyanido-bridged {Dy2Pt3} molecules incorporating heteroligand PtIV linkers

Abstract

The interest in the generation of photoluminescence in lanthanide(III) single-molecule magnets (SMMs) is driven by valuable magneto-optical correlations as well as perspectives toward magnetic switching of emission and opto-magnetic devices linking SMMs with optical thermometry. In the pursuit of enhanced magnetic anisotropy and optical features, the key role is played by suitable ligands attached to the 4f metal ion. In this context, cyanido complexes of d-block metal ions, serving as expanded metalloligands, are promising. We report two novel discrete coordination systems serving as emissive SMMs, {[Dy^III(H₂O)₃(tmpo)₃]₂[Pt^IVBr₂(CN)₄]₃}·2H₂O (1) and {[Dy^III(H₂O)(tmpo)₄]₂[Pt^IVBr₂(CN)₄]₃}·2CH₃CN (2) (tmpo = trimethylphosphine oxide), obtained by combining Dy^III complexes with uncommon dibromotetracyanidoplatinate(IV) ions, [Pt^IVBr₂(CN)₄]²⁻. They are built of analogous Z-shaped cyanido-bridged {Dy₂Pt₃} molecules but differ in the coordination number of Dy^III (C.N. = 8 in 1, C.N. = 7 in 2) and the number of coordinated tmpo ligands (three in 1, four in 2) which is related to the applied solvents. As a result, both compounds reveal Dy^III-centred slow magnetic relaxation but only 1 shows SMM character at zero dc field, while 2 is a field-induced SMM. The relaxation dynamics in both systems is governed by the Raman relaxation mechanism. These effects were analysed using ac magnetic data and the results of the ab initio calculations with the support of magneto-optical correlations based on low-temperature high-resolution emission spectra. Our findings indicate that heteroligand halogeno-cyanido Pt^IV complexes are promising precursors for emissive SMMs with the further potential of sensitivity to external stimuli that may be related to the lability of the axially positioned halogeno ligands.