Probing decoherence in molecular 4f qubits.

We probe herein the fundamental factors that induce decoherence in ensembles of molecular magnetic materials. This is done by pulse Electron Paramagnetic Resonance measurements at X-band (∼9.6 GHz) on single crystals of Gd@Y(trensal) at 0.

Dinuclear Dysprosium Compounds: The Importance of Rigid Bridges.

We report the synthesis, structures and magnetic behaviour of two isostructural dinuclear Dy complexes where the metal ions of a previously reported monomeric building block are connected by a peroxide (O ) or a pair of fluoride (2×F) bridges. The nature of the bridge determines the distance between the metal ion dipoles leading to a dipolar coupling in the peroxido bridged compound of only ca. 70 % of that in the bis-fluorido bridged dimer.

A new family of heterometallic [CuM] (M = Gd, Tb, Dy and Y) clusters derived from the combined use of selected pyridyl poly-alcohol ligands.

The combined use of 2-(2-pyridyl)-1,3-propane-diol (pypdH) and 2-hydroxymethyl-2-(2-pyridyl)-1,3-propane-diol (pyptH) in Cu/4f chemistry has afforded a new family of isostructural [CuM(pypt)(pypdH)(NO)] [M = Gd (1), Tb (2), Dy (3), and Y (4)] complexes. These compounds are based on an unprecedented three-layered symmetric [CuM(μ-OR)] structural core, formed from the connection of the metal ions by bridging alkoxide arms of the organic ligands. Direct current magnetic susceptibility studies for complexes 1-3 revealed the presence of dominant ferromagnetic exchange interactions, suggesting the existence of large spin ground state values.

Proof-of-Concept Quantum Simulator Based on Molecular Spin Qudits.

The use of -level qudits instead of two-level qubits can largely increase the power of quantum logic for many applications, ranging from quantum simulations to quantum error correction. Magnetic molecules are ideal spin systems to realize these large-dimensional qudits. Indeed, their Hamiltonian can be engineered to an unparalleled extent and can yield a spectrum with many low-energy states.

A bis-calix[4]arene-supported [CuII16] cage.

Reaction of 2,2'-bis--Bu-calix[4]arene (HL) with Cu(NO)·3HO and -methyldiethanolamine (Me-deaH) in a basic dmf/MeOH mixture affords [CuII16(L)(Me-dea)(μ-NO)(μ-OH)(dmf)(MeOH)(HO)](HL)·16dmf·4HO (4), following slow evaporation of the mother liquor. The central core of the metallic skeleton describes a tetracapped square prism, [Cu], in which the four capping metal ions are the Cu ions housed in the calix[4]arene polyphenolic pockets. The [CuII8] square prism is held together "internally" by a combination of hydroxide and nitrate anions, with the -methyldiethanolamine co-ligands forming dimeric [CuII2] units which edge-cap above and below the upper and lower square faces of the prism.

Long aliphatic chain derivatives of trigonal lanthanide complexes.

The trigonal lanthanide complexes LnL (HL = tris(((3-formyl-5-methylsalicylidene)amino)ethyl)amine) contain three pendant aldehyde groups and are known to react with primary amines. Reacting LnL (Ln = Yb, Lu) with 1-octadecylamine yields the novel aliphatic lanthanide complexes LnL (HL = tris(((3-(1-octadecylimine)-5-methylsalicylidene)amino)ethyl)amine) where the three aldehyde groups are transformed to 1-octadecylimine groups. Herein the syntheses, structural characterisation and magnetic properties of LnL are presented.

Dipolar-Coupled Entangled Molecular 4f Qubits.

We demonstrate by use of continuous wave- and pulse-electron paramagnetic resonance spectroscopy on oriented single crystals of magnetically dilute Yb ions in YbLu(trensal) that molecular entangled two-qubit systems can be constructed by exploiting dipolar interactions between neighboring Yb centers. Furthermore, we show that the phase memory time and Rabi frequencies of these dipolar-interaction-coupled entangled two-qubit systems are comparable to the ones of the corresponding single qubits.

Spin-Lattice Relaxation Decoherence Suppression in Vanishing Orbital Angular Momentum Qubits.

Multifrequency electron paramagnetic resonance spectroscopy on oriented single crystals of magnetically dilute Gd(III) ions in GdY(trensal) is used to determine the Hamiltonian parameters of the ground term and its phase memory time, , characterizing its coherent spin dynamics. The vanishing orbital angular momentum of the term makes it relatively insensitive to spin-lattice relaxation mediated by magnetoelastic coupling and leads to a of 12 μs at 3 K, which is not limited by spin-lattice relaxation.

Correction: The coordination chemistry of -butylcalix[4]arene with paramagnetic transition and lanthanide metal ions: an Edinburgh Perspective.

Correction for 'The coordination chemistry of -butylcalix[4]arene with paramagnetic transition and lanthanide metal ions: an Edinburgh Perspective' by Lucinda R. B. Wilson , , 2022, DOI: 10.

The coordination chemistry of -butylcalix[4]arene with paramagnetic transition and lanthanide metal ions: an Edinburgh Perspective.

The calix[4]arene scaffold is an extremely versatile supramolecular platform that has found widespread use across many research areas due to its synthetic versatility, controllable conformation, and the presence of cavities or clefts for tailorable guest binding. The tetraphenolic lower-rim of -butylcalix[4]arene in the cone conformation is ideal for binding a variety of paramagnetic transition and lanthanide metals, and in this Perspective we review our endeavours in using such complexes as metalloligands in the synthesis of polymetallic clusters that have fascinating structural and magnetic properties. By varying reactants, stoichiometries and reaction or crystallisation conditions it is possible to access an incredible range of clusters, all of which show consistent trends in coordination preferences and assembly behaviours.

Analysis of vibronic coupling in a 4f molecular magnet with FIRMS.

Vibronic coupling, the interaction between molecular vibrations and electronic states, is a fundamental effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect.

Magnetic Archimedean Tessellations in Metal-Organic Frameworks.

The self-assembly of lanthanide ions with ditopic organic spacers results in the formation of complex tiling patterns that mimic the structural motifs of quasi-periodic 2D materials. The linking of -{LnI} nodes (Ln = Gd, Dy) by both closed-shell and anion radicals of 4,4'-bipyridine affords rare examples of Archimedean tessellations in a metal-organic framework. We furthermore demonstrate the occurrence of sizable magnetic exchange interactions and slow relaxation of magnetization behavior in a complex tessellation pattern.

[(VO)MII5] (M = Ni, Co) Anderson wheels.

Heterometallic Anderson wheels of formula [(VO)MII5(hmp)Cl](ClO)·2MeOH (M = Ni, 1; Co, 2) have been synthesised from the solvothermal reaction of M(ClO)·6HO and VCl with hmpH (2-(hydroxymethyl)pyridine). The metallic skeleton describes a centred hexagon, with the two vanadyl ions sitting on opposing sides of the outer ring. Magnetic susceptibility and magnetisation measurements indicate the presence of both ferromagnetic and antiferromagnetic exchange interactions.

Exploiting host-guest chemistry to manipulate magnetic interactions in metallosupramolecular ML tetrahedral cages.

Reaction of Ni(OTf) with the bisbidentate quaterpyridine ligand results in the self-assembly of a tetrahedral, paramagnetic cage [Ni ]. By selectively exchanging the bound triflate from [OTf⊂Ni ](OTf) (), we have been able to prepare a series of host-guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MX⊂Ni ](OTf), where MX = MnCl (), CoCl (), CoBr (), NiCl (), and CuBr () or [MX⊂Ni ](OTf), where MX = FeCl () and FeBr (). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations.

Design of pure heterodinuclear lanthanoid cryptate complexes.

Heterolanthanide complexes are difficult to synthesize owing to the similar chemistry of the lanthanide ions. Consequently, very few purely heterolanthanide complexes have been synthesized. This is despite the fact that such complexes hold interesting optical and magnetic properties.

Hard X-ray magnetochiral dichroism in a paramagnetic molecular 4f complex.

Magnetochiral dichroism (MΧD) originates in the coupling of local electric fields and magnetic moments in systems where a simultaneous break of space parity and time-reversal symmetries occurs. This magnetoelectric coupling, displayed by chiral magnetic materials, can be exploited to manipulate the magnetic moment of molecular materials at the single molecule level. We demonstrate herein the first experimental observation of X-ray magnetochiral dichroism in enantiopure chiral trigonal single crystals of a chiral mononuclear paramagnetic lanthanide coordination complex, namely, holmium oxydiacetate, at the Ho L-edge.

[CrNi] Heterometallic Coordination Cubes.

Three new heterometallic [CrNi] coordination cubes of formulae [CrNiL(HO)](NO) (), [CrNiL(MeCN)(HO)](ClO) (), and [CrNiLCl] () (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrL] and the corresponding Ni salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight Cr and six Ni ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on () reveal weak ferromagnetic interactions between the Cr and Ni ions, with = + 0.

Functionalized Trigonal Lanthanide Complexes: A New Family of 4f Single-Ion Magnets.

We report the synthesis, characterization, and magnetic properties of eight neutral functionalized trigonal lanthanide coordination complexes LnL with Ln = Gd (), Tb (), Dy (), Ho (), Er (), Tm (), Yb (), Lu (). These were prepared through a one-pot synthesis where, first, the ligand HL was synthesized through a Schiff base reaction of tris(2-aminoethyl)amine with 2,6-diformyl--cresol. Following addition of Ln(OTf)·HO and base, LnL was obtained.

Lanthanide cryptate monometallic coordination complexes.

We report the synthesis, characterisation and magnetic properties of six novel neutral lanthanide cryptate coordination complexes. Reaction of 2,6-diformyl-4-methylphenol, tris(2-aminoethyl)amine and Ln(OTf)3·9H2O in the ratio 3 : 2 : 1, respectively, and in the presence of base affords the isolation of the six complexes LnL·4H2O (Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5) and Yb (6)), with H3L being the cryptand N[(CH2)2N[double bond, length as m-dash]CH-R-CH[double bond, length as m-dash]N-(CH2)2]3N (R = m-C6H2OH-2-Me-5). Powder X-ray diffraction confirms that the six complexes are isostructural.

Correction: Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

[This corrects the article DOI: 10.1039/C8SC03170C.].

Molecular multifunctionality preservation upon surface deposition for a chiral single-molecule magnet.

The synthesis and characterization of a chiral, enneanuclear Mn(iii)-based, Single-Molecule Magnet, [MnO(Me-sao)(L)(MeO)(MeOH)]Cl (; Me-saoH = methylsalicylaldoxime, HL = lipoic acid) is reported. Compound crystallizes in the orthorhombic 222 space group and consists of a metallic skeleton describing a defect super-tetrahedron missing one vertex. The chirality of the [Mn ] core originates from the directional bridging of the Me-sao ligands the -N-O- oximate moieties, which define a clockwise () or counter-clockwise () rotation in both the upper [Mn ] and lower [Mn ] subunits.

Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy(bpm)(fod)] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2'-bipyrimidine). calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry.

Coherent Manipulation of a Molecular Ln-Based Nuclear Qudit Coupled to an Electron Qubit.

We demonstrate that the [Yb(trensal)] molecule is a prototypical coupled electronic qubit-nuclear qudit system. The combination of noise-resilient nuclear degrees of freedom and large reduction of nutation time induced by electron-nuclear mixing enables coherent manipulation of this qudit by radio frequency pulses. Moreover, the multilevel structure of the qudit is exploited to encode and operate a qubit with embedded basic quantum error correction.

A simple methodology for constructing ferromagnetically coupled Cr(iii) compounds.

A large family of chromium(iii) dimers has been synthesised and magneto-structurally characterised using a combination of carboxylate and diethanolamine type ligands. The compounds have the general formula [Cr2(R1-deaH)2(O2CR2)Cl2]Cl where R1 = Me and R2 = H (1), Me (2), CMe3 (3), Ph (4), 3,5-(Cl)2Ph (5), (Me)5Ph (6), R1 = Et and R2 = H (7), Ph (8). The compound [Cr2(Me-deaH)2Cl4] (9) was synthesised in order to study the effect of removing/adding the carboxylate bridge on the observed magnetic behaviour.

Chemical tunnel-splitting-engineering in a dysprosium-based molecular nanomagnet.

Total control over the electronic spin relaxation in molecular nanomagnets is the ultimate goal in the design of new molecules with evermore realizable applications in spin-based devices. For single-ion lanthanide systems, with strong spin-orbit coupling, the potential applications are linked to the energetic structure of the crystal field levels and quantum tunneling within the ground state. Structural engineering of the timescale of these tunneling events via appropriate design of crystal fields represents a fundamental challenge for the synthetic chemist, since tunnel splittings are expected to be suppressed by crystal field environments with sufficiently high-order symmetry.