Multifunctional lanthanide-based single-molecule magnets exhibiting luminescence thermometry and photochromic and ferroelectric properties.

Lanthanide-based single-molecule magnets (SMMs) have captivated the attention of researchers due to their great potential application in quantum information processing, storage, spintronics etc. Recent years have witnessed continuous breakthroughs in the field of SMMs, which make them very promising to be used in future practical functional applications. However, there remain formidable obstacles involving suppression of the quantum tunneling of magnetization (QTM) to maximize magnetic anisotropy, integrating and applying them in devices etc. Meanwhile, multifunctional 4f-based SMMs, which combine optical and electronic properties, are attracting increasing attention. This will provide a new perspective for future multifunctional device applications and deep insight into understanding the magnetic relaxation behavior as well. In this frontier article, we highlight the research that recently emerged involving 4f-based SMMs in combination with luminescence thermometry and photochromic and ferroelectric properties, respectively.

Highly Performant Electromagnetic Absorption at the X Band Based on Co@NCS/Ti3C2Tx Composites.

Electromagnetic waves at the X band (8.2-12.4 GHz) play significant roles in military applications such as radar, satellite, and wireless communication. However, within this band range, the developed performance of electromagnetic absorption (EMA) is still unsatisfied, and it is hard to settle the corresponding problems on radar stealth and electromagnetic pollution. Herein, we demonstrate a state-of-the-art EMA property of -82.6 dB at 8.24 GHz with 2.57 mm thickness and 30 wt % paraffin filling ratio. For this purpose, an optimal Co@NCS/Ti3C2Tx composite is prepared by an electrostatic self-assembly approach through compelling Co-loading of nitrogen-doped carbon sheets (Co@NCS) derived from the pyrolysis of ZIF-67 (CoZn) with 2D Ti3C2Tx MXene nanosheets. Experimental results show that the highly efficient EMA performance of this Co@NCS/Ti3C2Tx composite originates from the large surface area for multiple reflection and electromagnetic wave scattering, from abundant defects sites for dipole and interfacial polarization, and from the optimizing impedance matching by the combination of Co magnetic nanoparticles and conductive NCS/Ti3C2Tx composite. These results confirm that the as-fabricated composites possess scientific and practical values for EMA applications at the X band, paving the way for developing highly performant electromagnetic absorbers toward specific microwave bands.

One-Dimensional Chain Viologen-Based Lanthanide Multistimulus-Responsive Materials with Photochromism, Photoluminescence, Photomagnetism, and Ammonia/Amine Vapor Sensing.

In this work, a series of novel multistimulus-responsive lanthanide coordination polymers {[LnL(H2O)4]Cl3·3H2O}n (Ln = Dy, Tb, Eu) constructed using a dicarboxylic acid viologen derivative L (L = N,N'-4,4'-bipyridiniodipropionate) and LnCl3·6H2O were prepared. All materials showed positive responses to UV light, and the photochromic phenomena accompanied by significant photoquenching of photoluminescence could be observed through a photoelectron transfer mechanism. Strikingly, the Dy analogue displayed photomagnetic behavior, as well as responded positively to small molecules of inorganic ammonia/organic amines. Furthermore, the good photoresponsive and ammonia/amine vapor-responsive properties of the Dy-based material were further fulfilled in dual-function papers involving erasable inkless printing and visual amine detection applications. This work aims to advance the development of multistimulus-responsive multifunctional materials incorporating viologen derivates and versatile lanthanide ions and further enriches the research in this field.

Di- and Tetranuclear Dysprosium Single-Molecule Magnets Bridged by Unprecedentedly Disassembled Nitrogen-Enriched Tetrazine Derivatives.

A series of di- and tetranuclear lanthanide complexes with the formulas [Dy2bmzch(tmhd)5 (CH3OH)]·CH3OH (1), [Dy2bmzch(dbm)4 (CH3O)(CH3OH)]·0.5CH3OH·0.5H2O (2), and Dy4bmzch(btfa)10 (3), where tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, dbm = dibenzoylmethane, btfa = benzoyltrifluoroacetone, and bmzch = (Z)-N-[(E)-pyrimidin-2-ylmethylene]pyrimidine-2-carbohydrazonate, were structurally and magnetically characterized. More strikingly, although the nitrogen-enriched bridged ligand 3,6-di(pyrimidin-2-yl)-1,2,4,5-tetrazine (bmtz) was initially adopted, the structures of the complexes obtained indicated that bmtz underwent unprecedented asymmetric ring opening and generated a new ligand bmzch. Combined with different ß-diketonates, di- and tetranuclear dysprosium complexes were constructed in which the structural patterns are very sensitive to the selected ß-diketonates. In view of this, the bilateral and unilateral dinuclear Dy2 complexes 1 and 2 and tetranuclear Dy4 complex 3 were obtained by choosing different ß-diketonates. Magnetic test results reveal that both complexes 1 and 3 showcase typical slow magnetic relaxation behavior without an external direct-current field and the effective energy barrier of the latter is almost twice that of the former, while complex 2 only displays in-field single-molecule-magnetic behavior. Also of note is that these are the first tetrazine-type dysprosium-based single-molecule-magnets undergoing in situ asymmetric ring-opening reaction of this ligand that are formed.