The effect of co-ligands on the performance of single-molecule magnet behaviours in a family of linear trinuclear Zn-Dy-Zn complexes with a compartmental Schiff base.

We present herein magneto-structural studies of three heterometallic Zn2Dy complexes: [Zn2Dy(L)2Cl2(H2O)](ClO4)·4H2O (1), [Zn2Dy(L)2Br2(H2O)](ClO4)·4H2O (2) and [Zn2Dy(L)2(OAc)I(H2O)]I3·4H2O (3), utilizing a new Schiff base ligand, N,N'-bis(3-methoxy-5-methylsalicylidene)-1,2-diaminocyclohexane (H2L). Complexes 1 and 2 exhibit remarkable magnetic relaxation behaviour with relatively high energy barriers in zero field (Ueff: 244 K for 1 and 211 K for 2) and notable hysteresis temperatures, despite the low local geometric symmetry around the central DyIII ions. The SMM performance of these complexes is further enhanced under an applied magnetic field, with Ueff increasing to 309 K for 1 and 269 K for 2, positioning them as elite members within the Zn-Dy SMM family. These findings emphasize the substantial influence of remote modulation on ZnII beyond the first coordination sphere of DyIII ions on their dynamic magnetic relaxation properties. Ab initio studies demonstrate that the relative orientation of the phenoxo-oxygen donor atoms around the DyIII ion is critical for determining the magnetic anisotropy and relaxation dynamics in these systems. Additionally, experimental and theoretical investigations reveal that the coordination of the bridging acetate towards the hard plane, combined with significant distortion from the ideal ZnO2Dy diamond core arrangement caused by the acetate ion, results in low magnetic anisotropy in complex 3, thereby leading to field-induced SMM behaviour. Overall, this study unveils the effects of co-ligands on the SMM performance in a series of linear trinuclear Zn-Dy-Zn complexes, which exhibit low local geometric symmetry around the DyIII centres.

Synthesis and Optical Properties of a Novel Hybrid Nanosystem Based on Covalently Modified nSiO2 Nanoparticles with a Curcuminoid Molecule.

A new curcuminoid molecule (3) has been designed and synthesized, containing a central -(CH2)2-COOH chain at the α carbon of the keto-enol moiety in the structure. The carboxylic acid group is added to react with exposed amino groups on silica oxide nanoparticles (nSiO2), forming an amide bond to attach the curcuminoid moiety to the nSiO2 covalently. The Kaiser test quantifies the functionalization degree, yielding 222 µmol of curcuminoid per gram of nanoparticles. The synthesized hybrid nanosystem, nSiO2-NHCO-CCM, displays significant emission properties, with a maximum emission at 538 nm in dichloromethane, similar to curcuminoid 1 (without the central chain), which emits at 565 nm in the same solvent. Solvent-induced spectral effects on the absorption and emission bands of the new hybrid nanosystem are confirmed, similar to those observed for the free curcuminoid (1). The new nanosystem is evaluated in the presence of kerosene in water, showing an emission band at 525 nm as a detection response. The ability of nSiO2-NHCO-CCM to change its fluorescence when interacting with kerosene in water is notable, as it overcomes the limitation caused by the insolubility of free curcuminoid 1 in water, allowing for the exploitation of its properties when connected to the water-stable nanosystem for future detection studies.

Understanding Single-Molecule Magnet properties of lanthanide complexes from 4f orbital splitting.

We present an approach for connecting the magnetic anisotropy of lanthanide mononuclear complexes with their f-orbital splitting for both idealized and real coordination environments. Our proposal is straightforward to apply and provides sensible estimations of the energy spacing of the ground multiplet for axial magnetic systems. This energy splitting controls Single-Molecule Magnet properties of lanthanide complexes, determining key parameters such as the demagnetization energy barrier (Ueff). Importantly, this approach is consistent with the current paradigm of oblate and prolate preferences for the distribution of the f-electron density, but delivers a finer description for ions belonging to the same group (e.g. the oblates TbIII and DyIII). The model provides simple explanations for some general trends observed experimentally (e.g. the low barriers for ErIII complexes in comparison to DyIII or the large barriers observed for cyclopentadienyl DyIII complexes in comparison with other ligands based on organometallic rings), contributing as a valuable tool to expand our description of ligand field effects in lanthanide-based SMMs.