An 'Intermetallic' Molecular Nanomagnet with the Lanthanide Coordinated Only by Transition Metals

The best performing molecular nanomagnets are currently designed by carefully arranging p-element donor atoms (usually carbon, nitrogen and/or oxygen) around the central magnetic ion. Inspired by the structure of the hardest intermetallic magnet SmCo5, we have demonstrated a nanomagnetic molecule where the central lanthanide (Ln) ion Er is coordinated solely by three transition metal (TM) ions in a perfectly trigonal planar fashion. The molecule [Er(ReCp2)3] (ErRe3) constitutes the first example of a molecular nanomagnet (MNM; or single molecule magnet SMM) with unsupported Ln-TM bonds and paves the way towards molecular intermetallics with strong direct magnetic exchange interactions. Such interactions are believed to be crucial for quenching the quantum tunneling of magnetization which limits the application of Ln-SMMs as sub-nanometer magnetic memory units.

Counteracting dephasing in Molecular Nanomagnets by optimized qudit encodings

Molecular Nanomagnets may enable the implementation of qudit-based quantum error-correction codes which exploit the many spin levels naturally embedded in a single molecule, a promising step towards scalable quantum processors. To fully realize the potential of this approach, a microscopic understanding of the errors corrupting the quantum information encoded in a molecular qudit is essential, together with the development of tailor-made quantum error correction strategies. We address these central points by first studying dephasing effects on the molecular spin qudit produced by the interaction with surrounding nuclear spins, which are the dominant source of errors at low temperatures. Numerical quantum error correction codes are then constructed, by means of a systematic optimization procedure based on simulations of the coupled system-bath dynamics, that provide a striking enhancement of the coherence time of the molecular computational unit. The sequence of pulses needed for the experimental implementation of the codes is finally proposed.

New Materials and Effects in Molecular Nanomagnets

Molecular magnets are a relatively new class of purely organic or metallo-organic materials, showing magnetism even without an external magnetic field. This interdisciplinary field between chemistry and physics has been gaining increased interest since the 1990s. While bulk molecular magnets are usually hard to build because of their molecular structures, low-dimensional molecular magnets are often easier to construct, down to dot-like (zero-dimensional) structures, which are investigated by different scanning probe technologies. On these scales, new effects such as superparamagnetic behavior or coherent switching during magnetization reversal can be recognized. Here, we give an overview of the recent advances in molecular nanomagnets, starting with single-molecule magnets (0D), typically based on Mn12, Fe8, or Mn4, going further to single-chain magnets (1D) and finally higher-dimensional molecular nanomagnets. This review does not aim to give a comprehensive overview of all research fields dealing with molecular nanomagnets, but instead aims at pointing out diverse possible materials and effects in order to stimulate new research in this broad field of nanomagnetism.

Near-Infrared Emissive Cyanido-Bridged {YbFe2} Molecular Nanomagnets Sensitive to the Nitrile Solvents of Crystallization

One of the pathways toward luminescent single-molecule magnets (SMMs) is realized by the self-assembly of lanthanide(3+) ions with cyanido transition metal complexes. We report a novel family of emissive SMMs, {YbIII(4-pyridone)4[FeII(phen)2(CN)2]2}(CF3SO3)3·solv (solv = 2MeCN, 1·MeCN; 2AcrCN, 1·AcrCN; 2PrCN, 1·PrCN; 2MalCN·1MeOH; 1·MalCN; MeCN = acetonitrile, AcrCN = acrylonitrile, PrCN = propionitrile, MalCN = malononitrile). They are based on paramagnetic YbIII centers coordinating diamagnetic [FeII(phen)2(CN)2] metalloligands but differ in the nitrile solvents of crystallization. They exhibit a field-induced slow magnetic relaxation dominated by a Raman process, without an Orbach relaxation as indicated by AC magnetic data and the ab initio calculations. The Raman relaxation is solvent-dependent as represented by the power “n” of the BRamanTn contribution varying from 3.07(1), to 2.61(1), 2.37(1), and 1.68(4) for 1·MeCN, 1·PrCN, 1·AcrCN, and 1·MalCN, respectively, while the BRaman parameter adopts the opposite trend. This was correlated with the variation of phonon modes schemes, including the number of available vibrational modes and their energies, dependent on the increasing complexity of the applied nitrile. 1·MeCN and 1·MalCN show the additional T-independent relaxation assignable to dipole-dipole interactions as confirmed by its suppression in 1·AcrCN and 1·PrCN revealing longer Yb–Yb distances and the disappearance in the LuIII-diluted 1·MeCN@Lu. All compounds exhibit YbIII–centered near-infrared photoluminescence sensitized by organic ligands.

Data mining, dashboards and statistics: a powerful framework for the chemical design of molecular nanomagnets

Three decades of intensive research in molecular nanomagnets have brought the magnetic memory in molecules from liquid helium to liquid nitrogen temperature. The enhancement of this operational temperature relies on a wise choice of the magnetic ion and the coordination environment. However, serendipity, oversimplified theories and chemical intuition have played the main role. In order to establish a powerful framework for statistically driven chemical design, we collected chemical and physical data for lanthanide-based nanomagnets to create a catalogue of over 1400 published experiments, developed an interactive dashboard (SIMDAVIS) to visualise the dataset, and applied inferential statistical analysis to it. We found that the effective energy barrier derived from the Arrhenius equation displays an excellent correlation with the magnetic memory, and that among all chemical families studied, only terbium bis-phthalocyaninato sandwiches and dysprosium metallocenes consistently present magnetic memory up to high temperature, but that there are some promising strategies for improvement.

SHG-active NIR-emissive molecular nanomagnets generated in layered neodymium(III)-octacyanidometallate(IV) frameworks

Lanthanide(III) single-molecule magnets (Ln-SMMs) offer the fruitful conjunction of magnetic and photoluminescent properties originating from their single-ion anisotropy and emissive f-f electronic transitions. The flexibility of lanthanide(III)-based coordination systems is...

Insights on the coupling between vibronically active molecular vibrations and lattice phonons in molecular nanomagnets

We provide a simple and insightful model to study the coupling of local vibrational modes with long-wavelength longitudinal and transverse phonons in the clock-like spin qubit [Ho(W5O18)2]9−.

Enhancing magnetic performance of pyrazine-N-oxide bridged dysprosium chains through controlled variation of ligand coordination modes

While assembling superparamagnetic units in a controlled manner is crucial for future applications of molecular nanomagnets, it still constitutes a formidable challenge to optimize their magnetic properties while achieving a...