Practical implementation of highly coherent molecular spin qubits for challenging technological applications, such as quantum information processing or quantum sensing, requires precise organization of electronic qubit molecular components into extended frameworks. Realization of spatial control over qubit-qubit distances can be achieved by coordination chemistry approaches through an appropriate choice of the molecular building blocks. However, translating single qubit molecular building units into extended arrays does not guarantee a priori retention of long quantum coherence and spin-lattice relaxation times due to the introduced modifications over qubit-qubit reciprocal distances and molecular crystal lattice phonon structure. In this work, we report the preparation of a three-dimensional (3D) metal-organic framework (MOF) based on vanadyl qubits, [VO(TCPP-Zn-bpy)] (TCPP = tetracarboxylphenylporphyrinate; bpy = 4,4'-bipyridyl) (1), and the investigation of how such structural modifications influence qubits' performances. This has been done through a multitechnique approach where the structure and properties of a representative molecular building block of formula [VO(TPP)] (TPP = tetraphenylporphyrinate) (2) have been compared with those of the 3D MOF 1. Pulsed electron paramagnetic resonance measurements on magnetically diluted samples in titanyl isostructural analogues revealed that coherence times are retained almost unchanged for 1 with respect to 2 up to room temperature, while the temperature dependence of the spin-lattice relaxation time revealed insights into the role of low-energy vibrations, detected through terahertz spectroscopy, on the spin dynamics.

The unique electronic and magnetic properties of lanthanide molecular complexes place them at the forefront of the race toward high-temperature single-molecule magnets and magnetic quantum bits. The design of compounds of this class has so far being almost exclusively driven by static crystal field considerations, with an emphasis on increasing the magnetic anisotropy barrier. Now that this guideline has reached its maximum potential, a deeper understanding of spin-phonon relaxation mechanisms presents itself as key in order to drive synthetic chemistry beyond simple intuition. In this work, we compute relaxation times fully ab initio and unveil the nature of all spin-phonon relaxation mechanisms, namely Orbach and Raman pathways, in a prototypical Dy single-molecule magnet. Computational predictions are in agreement with the experimental determination of spin relaxation time and crystal field anisotropy, and show that Raman relaxation, dominating at low temperature, is triggered by low-energy phonons and little affected by further engineering of crystal field axiality. A comprehensive analysis of spin-phonon coupling mechanism reveals that molecular vibrations beyond the ion’s first coordination shell can also assume a prominent role in spin relaxation through an electrostatic polarization effect. Therefore, this work shows the way forward in the field by delivering a novel and complete set of chemically sound design rules tackling every aspect of spin relaxation at any temperature.

The selection of molecular spin qubits with a long coherence time, T m , is a central task for implementing molecule-based quantum technologies. Even if a sufficiently long T m can be achieved through an efficient synthetic strategy and ad hoc experimental measurement procedures, many factors contributing to the loss of coherence still need to be thoroughly investigated and understood. Vibrational properties and nuclear spins of hydrogens are two of them. The former plays a paramount role, but a detailed theoretical investigation aimed at studying their effects on the spin dynamics of molecular complexes such as the benchmark phthalocyanine (Pc) is still missing, whereas the effect of the latter deserves to be examined in detail for such a class of compounds. In this work, we adopted a combined theoretical and experimental approach to investigate the relaxation properties of classical [Cu(Pc)] and a Cu II complex based on the ligand tetrakis(thiadiazole)porphyrazine (H 2 TTDPz), characterized by a hydrogen-free molecular structure. Systematic calculations of molecular vibrations exemplify the effect of normal modes on the spin–lattice relaxation process, unveiling a different contribution to T 1 depending on the symmetry of normal modes. Moreover, we observed that an appreciable T m enhancement could be achieved by removing hydrogens from the ligand.

We report here the synthesis of a new meso-meso (m-m) singly linked vanadyl-porphyrin dimer that crystallizes in two different pseudo-polymorphs. The single crystal continuous-wave Electron Paramagnetic Resonance investigation evidences a...

It is well assessed that the charge transport through a chiral potential barrier can result in spin-polarized charges. The possibility of driving this process through visible photons holds tremendous potential...

Hybrid architectures combining complementary quantum systems will be largely used in quantum technologies and the integration of different components is one of the key issues. Thanks to their long coherence times and the easy manipulation with microwave pulses, electron spins hold a potential for the realization of quantum memories. Here, we test diluted oxovanadium tetraphenyl porphyrin (VO(TPP)) as a prototypical molecular spin system for the Storage/Retrieval of microwave pulses when embedded into planar superconducting microwave resonators. We first investigate the efficiency of several pulse sequences in addressing the spins. The Carr-Purcell and the Uhrig Dynamical Decoupling enhance the memory time up to three times with three π pulses. We then successfully store and retrieve trains of up to 5 small pulses by using a single recovery pulse. These results demonstrate the memory capabilities of molecular spin ensembles when embedded into quantum circuits.

Magnetochiral dichroism (MChD) is a nonreciprocal manifestation of light−matter interaction that can be observed in chiral magnetized systems. It features a differential absorption of unpolarized light depending on the relative orientation of the magnetic field and the light wavevector and on the absolute configuration of the system. The relevance of this effect for optical readout of magnetic data calls for a complete understanding of the microscopic parameters driving MChD with an easy-accessible and nondamaging light source, such as visible light. For this purpose, here we report on MChD detected with visible light on a chiral magnetic helix formulated as [Mn III (cyclam)(SO 4 )]ClO 4 •H 2 O (cyclam = 1,4,8,11-tetraazacyclotetradecane) featuring antiferromagnetically coupled anisotropic Mn III ions. Alternate current susceptibility measurements revealed the existence of a single-chain magnet behavior hidden below the canted antiferromagnetism (T N = 5.8 K) already evidenced by direct current magnetometry. A detailed analysis of the optical absorption gives access to the value of the zero-field splitting parameter D (2.9 cm −1 ), which quantifies the magnetic anisotropy of the Mn III centers. Below the magnetic ordering temperature of the material, the MChD spectra exhibit intense absolute configuration dependent MChD signals reaching record values of ca. 12% of the absorbed intensity for the two electronic transitions most influenced by the spin−orbit coupling of the Mn III ion. These findings set a clear route toward the design and preparation of highly MChD-responsive molecular materials.

Improving the performance of molecular qubits is a fundamental milestone towards unleashing the power of molecular magnetism in the second quantum revolution. Taming spin relaxation and decoherence due to vibrations is crucial to reach this milestone, but this is hindered by our lack of understanding on the nature of vibrations and their coupling to spins. Here we propose a synergistic approach to study a prototypical molecular qubit. It combines inelastic X-ray scattering to measure phonon dispersions along the main symmetry directions of the crystal and spin dynamics simulations based on DFT. We show that the canonical Debye picture of lattice dynamics breaks down and that intra-molecular vibrations with very-low energies of 1-2 meV are largely responsible for spin relaxation up to ambient temperature. We identify the origin of these modes, thus providing a rationale for improving spin coherence. The power and flexibility of our approach open new avenues for the investigation of magnetic molecules with the potential of removing roadblocks toward their use in quantum devices.