Dual Structure of a Vanadyl-Based Molecular Qubit Containing a Bis(ß-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(ß-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 (1h) with a honeycomb structure and 46% of solvent-accessible voids quantitatively transforms over time into a monoclinic solvatomorph 1m and minor amounts of a triclinic solventless phase (1a). In a static magnetic field, 1h and 1m 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 Tm 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.

Spin-Lattice Relaxation and Spin-Phonon Coupling of ns1 Metal Ions at the Surface.

To use transition metal ions for spin-based applications, it is essential to understand fundamental contributions to electron spin relaxation in different ligand environments. For example, to serve as building blocks for a device, transition metal ion-based molecular qubits must be organized on surfaces and preserve long electron spin relaxation times, up to room temperature. Here we propose monovalent group 12 ions (Zn+ and Cd+) as potential electronic metal qubits with an ns1 ground state. The relaxation properties of Zn+ and Cd+, stabilized at the interface of porous aluminosilicates, are investigated and benchmarked against vanadium (3d1) and copper (3d9) ions. The spin-phonon coupling has been evaluated through DFT modeling and found to be negligible for the ns1 states, explaining the long coherence time, up to 2 µs, at room temperature. These so far unexplored metal qubits may represent viable candidates for room temperature quantum operations and sensing.

(η8-Cyclooctatetraene)(η5-fluorenyl)titanium: a processable molecular spin qubit with optimized control of the molecule-substrate interface.

Depositing single paramagnetic molecules on surfaces for sensing and quantum computing applications requires subtle topological control. To overcome issues that are often encountered with sandwich metal complexes, we exploit here the low symmetry architecture and suitable vaporability of mixed-sandwich [FluTi(cot)], Flu = fluorenyl, cot = cyclooctatetraene, to drive submonolayer coverage and select an adsorption configuration that preserves the spin of molecules deposited on Au(111). Electron paramagnetic resonance spectroscopy and ab initio quantum computation evidence a d z 2 ground state that protects the spin from phonon-induced relaxation. Additionally, computed and measured spin coherence times exceed 10 µs despite the molecules being rich in hydrogen. A thorough submonolayer investigation by scanning tunneling microscopy, X-ray photoelectron and absorption spectrocopies and X-ray magnetic circular dichroism measurements supported by DFT calculations reveals that the most stable configuration, with the fluorenyl in contact with the metal surface, prevents titanium(iii) oxidation and spin delocalization to the surface. This is a necessary condition for single molecular spin qubit addressing on surfaces.

Quantum spin coherence and electron spin distribution channels in vanadyl-containing lantern complexes.

We herein investigate the heterobimetallic lantern complexes [PtVO(SOCR)4] as charge neutral electronic qubits based on vanadyl complexes (S = 1/2) with nuclear spin-free donor atoms. The derivatives with R = Me (1) and Ph (2) give highly resolved X-band EPR spectra in frozen CH2Cl2/toluene solution, which evidence the usual hyperfine coupling with the 51V nucleus (I = 7/2) and an additional superhyperfine interaction with the I = 1/2 nucleus of the 195Pt isotope (natural abundance ca. 34%). DFT calculations ascribe the spin density delocalization on the Pt2+ ion to a combination of π and δ pathways, with the former representing the predominant channel. Spin relaxation measurements in frozen CD2Cl2/toluene-d8 solution between 90 and 10 K yield Tm values (1-6 µs in 1 and 2-11 µs in 2) which compare favorably with those of known vanadyl-based qubits in similar matrices. Coherent spin manipulations indeed prove possible at 70 K, as shown by the observation of Rabi oscillations in nutation experiments. The results indicate that the heavy Group 10 metal ion is not detrimental to the coherence properties of the vanadyl moiety and that Pt-VO lanterns can be used as robust spin-coherent building blocks in materials science and quantum technologies.