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A new bis-hydroxyphenylpyrazolyl ligand, H4L, allows isolating and structurally characterizing vanadyl and titanyl dinuclear complexes (Bu4N)2[(MO)2(HL)2] (M = V, Ti). The weak dipolar coupling and relatively short quantum coherence of the divanadyl anions are optimal for a 2-qubit molecular architecture proposed to implement electron-mediated nuclear quantum simulations.

Magnetic molecules have been proposed as versatile building blocks for quantum computing and molecular spintronics devices. The molecular spin can be used to encode quantum information in qubits or even perform logic operations as quantum gates with unmatched reproducibility and scalability. In spintronics, that same molecular spin can be used to generate spin currents in molecular based spin filters, spin switches or spin valves in carbon-nanotube/molecule hybrids, among other applications. Several strategies have been followed to couple the magnetic molecules to carbon nanotubes: direct physisorption of the molecules, covalent bonding or encapsulation of the magnetic molecules. We have developed the synthesis of mechanically interlocked rotaxane-like SWCNT derivatives (MINTs), in which the ring-closing metathesis of a U-shape molecule around SWCNTs is templated. In particular, we fabricated Cu2+ and Co2+ metalloporphyrin dimer rings mechanically interlocked around carbon nanotubes to form magnetic MINTs (mMINT). Magnetic porphyrins are selected due to their recently proved suitability as qubits, even preserving their magnetic properties and quantum coherence on surfaces. The mechanical bond places the porphyrin magnetic cores in close contact with the SWCNT without disturbing the molecular spin nor the carbon nanotube structure. The magnetic properties of the metallic dimers are preserved upon formation the mechanically interlocked hybrid.

We present the magnetic properties of the metal-organic framework {[CoCxAPy]·2.15 H2O}n (Cx = bis(carboxypropyl)tetramethyldisiloxane; APy = 4,4`-azopyridine) (1) that builds up from the stacking of 2D coordination polymers. The 2D-coordination polymer in the bc plane is formed by the adjacent bonding of [CoCxAPy] 1D two-leg ladders with Co dimer rungs, running parallel to the c-axis. The crystal packing of 2D layers shows the presence of infinite channels running along the c crystallographic axis, which accommodate the disordered solvate molecules. The Co(II) is six-coordinated in a distorted octahedral geometry, where the equatorial plane is occupied by four carboxylate oxygen atoms. Two nitrogen atoms from APy ligands are coordinated in apical positions. The single-ion magnetic anisotropy has been determined by low temperature EPR and magnetization measurements on an isostructural compound {[Zn0.8Co0.2CxAPy]·1.5 CH3OH}n (2). The results show that the Co(II) ion has orthorhombic anisotropy with the hard-axis direction in the C2V main axis, lying the easy axis in the distorted octahedron equatorial plane, as predicted by the ab initio calculations of the g-tensor. Magnetic and heat capacity properties at very low temperatures are rationalized within a S* = 1/2 magnetic dimer model with anisotropic antiferromagnetic interaction. The magnetic dimer exhibits slow relaxation of the magnetization (SMM) below 6 K in applied field, with a tlf ≈ 2 s direct process at low frequencies, and an Orbach process at higher frequencies with U/kB = 6.7 ± 0.5 K. This compound represents a singular SMM MOF built-up of Co-dimers with an anisotropic exchange interaction.

We explore how to encode more than a qubit in vanadyl porphyrin molecules hosting a S = 1/2 electronic spin coupled to a I = 7/2 nuclear spin. The spin Hamiltonian and its parameters, as well as the spin dynamics, have been determined via a combination of electron paramagnetic resonance, heat capacity, magnetization and on-chip magnetic spectroscopy experiments performed on single crystals. We find low temperature spin coherence times of micro-seconds and spin relaxation times longer than a second. For sufficiently strong magnetic fields (B > 0.1 T, corresponding to resonance frequencies of 9–10 GHz) these properties make vanadyl porphyrin molecules suitable qubit realizations. The presence of multiple equispaced nuclear spin levels then merely provides 8 alternatives to define the ‘1’ and ‘0’ basis states. For lower magnetic fields (B < 0.1 T), and lower frequencies (<2 GHz), we find spectroscopic signatures of a sizeable electronuclear entanglement. This effect generates a larger set of allowed transitions between different electronuclear spin states and removes their degeneracies. Under these conditions, we show that each molecule fulfills the conditions to act as a universal 4-qubit processor or, equivalently, as a d = 16 qudit. These findings widen the catalogue of chemically designed systems able to implement non-trivial quantum functionalities, such as quantum simulations and, especially, quantum error correction at the molecular level.

We show that a [Er–Ce–Er] molecular trinuclear coordination compound is a promising platform to implement the three-qubit quantum error correction code protecting against pure dephasing, the most important error in magnetic molecules. We characterize it by preparing the [Lu–Ce–Lu] and [Er–La–Er] analogues, which contain only one of the two types of qubit, and by combining magnetometry, low-temperature specific heat and electron paramagnetic resonance measurements on both the elementary constituents and the trimer. Using the resulting parameters, we demonstrate by numerical simulations that the proposed molecular device can efficiently suppress pure dephasing of the spin qubits.

Artificial magnetic molecules can host several spin qubits, which could then implement small-scale algorithms. In order to become of practical use, such molecular spin processors need to increase the available computational space and warrant universal operations. Here, we design, synthesize and fully characterize dissymetric molecular dimers hosting either one or two Gadolinium(III) ions. The strong sensitivity of Gadolinium magnetic anisotropy to its local coordination gives rise to different zero-field splittings at each metal site. As a result, the [LaGd] and [GdLu] complexes provide realizations of distinct spin qudits with eight unequally spaced levels. In the [Gd2] dimer, these properties are combined with a Gd-Gd magnetic interaction, sufficiently strong to lift all level degeneracies, yet sufficiently weak to keep all levels within an experimentally accessible energy window. The spin Hamiltonian of this dimer allows a complete set of operations to act as a 64-dimensional all-electron spin qudit, or, equivalently, as six addressable qubits. Electron paramagnetic resonance experiments show that resonant transitions between different spin states can be coherently controlled, with coherence times TM of the order of 1 µs limited by hyperfine interactions. Coordination complexes with embedded quantum functionalities are promising building blocks for quantum computation and simulation hybrid platforms.

A comparative study of the homoleptic [M(CF3)4]− complexes of all three coinage metals (M=Cu, Ag, Au) reveals that homolytic M−C bond cleavage is favoured in every case upon excitation in the gas phase (CID‐MS2). Homolysis also occurs in solution by photochemical excitation. Transfer of the photogenerated CF3. radicals to both aryl and alkyl carbon atoms was also confirmed. The observed behaviour was rationalized by considering the electronic structure of the involved species, which all show ligand‐field inversion. Moreover, the homolytic pathway constitutes experimental evidence for the marked covalent character of the M−C bond. The relative stability of these M−C bonds was evaluated by energy‐resolved mass spectrometry (ERMS) and follows the order Cu

Molecular spin qubits have been shown to reach sufficiently long quantum coherence times to envision their use as hardware in quantum processors. These will however require their implementation in hybrid solid‐state devices for which the controlled localization and homogeneous orientation of the molecular qubits will be necessary. An alternative to isolated molecules that can ensure these key aspects is 2D framework in which the qubit would act as node. In this work, it is demonstrated that the isolated metalloporphyrin [Cu(H4TCPP)] molecule is a potential spin qubit, and maintains similar quantum coherence as node in a 2D [{CuTCPP}Zn2(H2O)2] metal–organic framework. Mono‐ and multilayer deposits of nanosheets of a similar 2D framework are then successfully formed following a modular method based on Langmuir–Schaefer conditions. The orientation of the {CuTCPP} qubit nodes in these nanosheets is homogeneous parallel to the substrate. These nanosheets are also formed with a control over the qubit concentration, i.e., by dilution with the unmetallated porphyrin. Eventually, 2D nanosheets are formed in situ directly on a substrate, through a simple protocol devised to reproduce the Langmuir–Schaefer conditions locally. Altogether these studies show that 2D spin qubit frameworks are ideal components to develop a hybrid quantum computing architecture.

Correction for 'Magnetic properties of the seven-coordinated nanoporous framework material Co(bpy)1.5(NO3)2 (bpy = 4,4'-bipyridine)' by Elena Bartolomé et al., Dalton Trans., 2012, 41, 10382-10389.

The practical realization of quantum computation schemes faces the challenge of increasing the number of qubits while keeping errors below a threshold that allows their coherent manipulation. This dilemma is of particular relevance for proposals involving electron spins. The implementation of even the simplest quantum algorithm implies coupling two or more of such qubits in a controlled manner. However, dipolar interactions between them are also an important source of decoherence, which has severely limited progressing beyond the realization of elemental two-qubit gates. Here, we explore a way to scale up quantum resources, without introducing additional decoherence, by integrating several electron spin qubits in a single magnetic ion with spin S > ½. This approach is illustrated with a Gd3+ ion trapped inside a suitably chosen polyoxoanion [Gd(H2O)P5W30O110]12- (GdW30, Fig 1). Electron paramagnetic resonance experiments (Fig. 1) have been performed on quasi-independent molecules diluted in a crystal of the diamagnetic isostructural derivative [Y(H2O)P5W30O110]12-. The full energy-level spectrum and the orientations of the magnetic anisotropy axes have been determined by means of continuouswave electron paramagnetic resonance experiments, using X-band (9–10 GHz) cavities and on-chip superconducting waveguides (0.1-14 GHz) and 1.5-GHz resonators. The results show that seven allowed transitions between the 2S + 1 spin states can be separately addressed. Spin coherence 1/T2 and spin-lattice relaxation 1/T1 rates have been measured for each of these transitions in properly oriented single crystals. The results suggest that quantum spin coherence is limited by residual dipolar interactions with neighbor electronic spins. Coherent Rabi oscillations have been observed for all transitions. The Rabi frequencies increase with microwave power and agree quantitatively with predictions based on the spin Hamiltonian of the molecular spin. We argue that the spin states of each Gd3

We study the quantum spin dynamics of nearly isotropic Gd3+ ions entrapped in polyoxometalate molecules and diluted in crystals of a diamagnetic Y3+ derivative. The full energy-level spectrum and the orientations of the magnetic anisotropy axes have been determined by means of continuous-wave electron paramagnetic resonance experiments, using X-band (9-10 GHz) cavities and on-chip superconducting waveguides and 1.5-GHz resonators. The results show that seven allowed transitions between the 2S+1 spin states can be separately addressed. Spin coherence T2 and spin-lattice relaxation T1 rates have been measured for each of these transitions in properly oriented single crystals. The results suggest that quantum spin coherence is limited by residual dipolar interactions with neighbor electronic spins. Coherent Rabi oscillations have been observed for all transitions. The Rabi frequencies increase with microwave power and agree quantitatively with predictions based on the spin Hamiltonian of the molecular spin. We argue that the spin states of each Gd3+ ion can be mapped onto the states of three addressable qubits (or, alternatively, of a d=8-level >qudit>), for which the seven allowed transitions form a universal set of operations. Within this scheme, one of the coherent oscillations observed experimentally provides an implementation of a controlled-controlled-NOT (or Toffoli) three-qubit gate.

The photosynthetic cytochrome c550 from the marine diatom Phaeodactylum tricornutum has been purified and characterized. Cytochrome c550 is mostly obtained from the soluble cell extract in relatively large amounts. In addition, the protein appeared to be truncated in the last hydrophobic residues of the C-terminus, both in the soluble cytochrome c550 and in the protein extracted from the membrane fraction, as deduced by mass spectrometry analysis and the comparison with the gene sequence. Interestingly, it has been described that the C-terminus of cytochrome c550 forms a hydrophobic finger involved in the interaction with photosystem II in cyanobacteria. Cytochrome c550 was almost absent in solubilized photosystem II complex samples, in contrast with the PsbO and Psb31 extrinsic subunits, thus suggesting a lower affinity of cytochrome c550 for the photosystem II complex. Under iron-limiting conditions the amount of cytochrome c550 decreases up to about 45% as compared to iron-replete cells, pointing to an iron-regulated synthesis. Oxidized cytochrome c550 has been characterized using continuous wave EPR and pulse techniques, including HYSCORE, and the obtained results have been interpreted in terms of the electrostatic charge distribution in the surroundings of the heme centre.