Dual Structure of a Vanadyl-Based Molecular Qubit Containing a Bis(β-diketonato) Ligand

We designed [VO(bdhb)] (1') as a new electronic qubit containing an oxovanadium(IV) ion (S = 1/2) embraced by a single bis(β-diketonato) ligand [H₂bdhb = 1,3-bis(3,5-dioxo-1-hexyl)benzene]. The synthesis afforded three different crystal phases, all of which unexpectedly contain dimers with formula [(VO)₂(bdhb)₂] (1). A trigonal form (1) with a honeycomb structure and 46% of solvent-accessible voids quantitatively transforms over time into a monoclinic solvatomorph 1 and minor amounts of a triclinic solventless phase (1). In a static magnetic field, 1 and 1 have detectably slow magnetic relaxation at low temperatures through quantum tunneling and Raman mechanisms. Angle-resolved electron paramagnetic resonance (EPR) spectra on single crystals revealed signatures of low-dimensional magnetic behavior, which is solvatomorph-dependent, being the closest interdimer V···V separations (6.7-7.5 Å) much shorter than intramolecular V···V distances (11.9-12.1 Å). According to ¹H diffusion ordered spectroscopy (DOSY) and EPR experiments, the complex adopts the desired monomeric structure in organic solution and its geometry was inferred from density functional theory (DFT) calculations. Spin relaxation measurements in a frozen toluene-d₈/CD₂Cl₂ matrix yielded T_m values reaching 13 μs at 10 K, and coherent spin manipulations were demonstrated by Rabi nutation experiments at 70 K. The neutral quasi-macrocyclic structure, featuring nuclear spin-free donors and additional possibilities for chemical functionalization, makes 1' a new convenient spin-coherent building block in quantum technologies.