David Aguilà

Heterodimetallic [LnLn′] Lanthanide Complexes: Toward a Chemical Design of Two-Qubit Molecular Spin Quantum Gates

A major challenge for realizing quantum computation is finding suitable systems to embody quantum bits (qubits) and quantum gates (qugates) in a robust and scalable architecture. An emerging bottom-up approach uses the electronic spins of lanthanides. Universal qugates may then be engineered by arranging in a molecule two interacting and different lanthanide ions. Preparing heterometallic lanthanide species is, however, extremely challenging. We have discovered a method to obtain [LnLn′] complexes with the appropriate requirements. Compound [CeEr] is deemed to represent an ideal situation. Both ions have a doubly degenerate magnetic ground state and can be addressed individually. Their isotopes have mainly zero nuclear spin, which enhances the electronic spin coherence. The analogues [Ce2], [Er2], [CeY], and [LaEr] have also been prepared to assist in showing that [CeEr] meets the qugate requirements, as revealed through magnetic susceptibility, specific heat, and EPR. Molecules could now be used for quantum information processing.

Lanthanide Contraction within a Series of Asymmetric Dinuclear [Ln2] Complexes

A complete isostructural series of dinuclear asymmetric lanthanide complexes has been synthesized by using the ligand 6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid (H3L). All complexes have the formula [Ln2(HL)2(H2L)(NO3)(py)(H2O)] (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14), Y (15); py = pyridine). Complexes of La to Yb and Y have been crystallographically characterized to reveal that the two metal ions are encapsulated within two distinct coordination environments of differing size. Whereas one site maintains the coordination number (nine) through the whole series, the other one increases from nine to ten owing to a change in the coordination mode of an NO3(-) ligand. This series offers a unique opportunity to study in detail the lanthanide contraction within complexes of more than one metal. This analysis shows that various representative parameters proportional to this contraction follow a quadratic decay as a function of the number n of f electrons. Slaters model for the atomic radii has been used to extract, from these decays, the shielding constant of 4f electrons. The average of O⋅⋅⋅O distances within the coordination polyhedra shared by both metals and of the Ln⋅⋅⋅Ln separations follow also a quadratic decay, therefore showing that such dependence holds also for parameters that receive the contribution of two lanthanide ions simultaneously. The magnetic behavior has been studied for all nondiamagnetic complexes. It reveals the effect of the spin-orbit coupling and a weak antiferromagnetic interaction between both metals. Photoluminescent studies of all the complexes in the series reveal a single broad emission band in the visible region, which is related to the coordinated ligand. On the other hand, the Nd, Er, and Yb complexes show features in the near-IR region due to metal-based transitions.

Synthesis and Properties of a Family of Unsymmetric Dinuclear Complexes of LnIII (Ln = Eu, Gd, Tb)

A new ligand has been synthesized with the aim of favoring distinct coordination environments within lanthanide polynuclear complexes. It has led to the formation of three unsymmetrical [Ln(III)(2)] (Ln = Gd, Tb, Eu) complexes, exhibiting weak antiferromagnetic coupling and, for Eu and Tb, high single-ion magnetic anisotropy. All of these attributes are necessary for these clusters to behave as possible 2qubit quantum gates.

Designed Topology and Site-Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

The ligand 1,3-bis[3-oxo-3-(2-hydroxyphenyl)propionyl]benzene (H(4)L), designed to align transition metals into tetranuclear linear molecules, reacts with M(II) salts (M=Ni, Co, Cu) to yield complexes with the expected [MMMM] topology. The novel complexes [Co(4)L(2)(py)(6)] (2; py=pyridine) and [Na(py)(2)][Cu(4)L(2)(py)(4)](ClO(4)) (3) have been crystallographically characterised. The metal sites in complexes 2 and 3, together with previously characterised [Ni(4)L(2)(py)(6)] (1), favour different coordination geometries. These have been exploited for the deliberate synthesis of the heterometallic complex [Cu(2)Ni(2)L(2)(py)(6)] (4). Complexes 1, 2, 3 and 4 exhibit antiferromagnetic interactions between pairs of metals within each cluster, leading to S=0 spin ground states, except for the latter cluster, which features two quasi-independent S=1/2 moieties within the molecule. Complex 4 gathers the structural and physical conditions, thus allowing it to be considered as prototype of a two-qbit quantum gate.

Calibrating the coordination chemistry tool chest: metrics of bi- and tridentate ligands

Bi- and multidentate ligands form part of the tools commonly used for designing coordination and supramolecular complexes with desired stereochemistries. Parameters and concepts usually employed include the normalized bite of bidentate ligands, their cis- or trans-coordinating ability, their rigidity or flexibility, or the duality of some ligands that can act in chelating or dinucleating modes. In this contribution we present a structural database study of over one hundred bi- and tridentate ligands that allows us to parametrize their coordinating properties and discuss the relevance of such parameters for the choice of coordination polyhedron or coordination sites.

A Molecular Chain of Four CoII Ions Stabilized by a Tris-Pyridyl/Bis-β-Diketonate Ligand

The synthesis and characterization of a tris-pyridyl/bis-β-diketone molecule (H2L) is reported. This compound acts as a hexadentate ligand towards CoII to facilitate the assembly of a tetranuclear molecular chain of closely spaced metals with formula [Co4L2(MeOH)8](NO3)4 (1), which exhibits a very flat [Co4L2]4+ platform, as determined by single-crystal X-ray diffraction crystallography. Complex 1 readily exchanges axial methanol ligands with water molecules. The bulk magnetization of the resulting hydrate, 1a, shows that the metals in the [Co4L2]4+ moiety exhibit spin-orbit coupling and antiferromagnetic exchange interactions.

Linear or cyclic clusters of Cu(II) with a hierarchical relationship

The polydentate ligand 2,6-bis(5-(2-hydroxyphenyl)-pyrazol-3-yl)-pyridine, H4L, exhibits a series of coordination pockets favoring the establishment of metal sequences with predetermined motifs, together with a degree of flexibility for the formation of clusters with various overall topologies. With Cu(II) under strong basic conditions it has a marked tendency to stabilize a cyclic [Cu16L8] cluster. The sequential formation of this compound via [Cu7L8](2-) intermediates, recognized in its structure, is suggested by crystallographic evidence, which shows the persistent formation of the complex salt (NBu4)2[Cu7L8] in the presence of the organic cation. Also, the crystallographic identification of the related cluster [Cu11L5(OH)2(py)12] from similar reaction conditions underscores the rich multiplicity of species attainable from this simple reaction system.

Molecular [Co(III)Co(II)] × 2 assemblies of a new bis-phenol/pyrazolyl ligand

Use of a novel multinucleating ligand in aerobic reactions with Co(II) affords two novel coordination assemblies exhibiting a rare linear [CoIII2CoII2] structure and novel structural features. The magnetic exchange within these unprecedented moieties is investigated.

Discrete and polymeric complexes formed from cobalt(II), 4,4′-bipyridine and 2-sulfoterephthalate: synthetic, crystallographic and magnetic studies

A series of five coordination compounds, namely, {[Co3(stp)2(bipy)(H2O)4]·2H2O}n, (1), {[Co3(stp)2(bipy)5(H2O)6]·4H2O}n, (2), [Co3(stp)2(bipy)4(H2O)10]·8H2O, (3), [Co(Hstp)2(Hbipy)2], (4) and {[Co(stp)2(H2O)2][Co(bipy)2(H2O)4]}·2Hbipy·2H2O, (5) have been synthesised hydrothermally, through the reaction of different molar ratios of 2-sulfoterephthalic acid monosodium salt, Na(H2stp), cobalt(II) nitrate hexahydrate and the N-donor ancillary co-ligand 4,4′-bipyridine (bipy). Due to the combination of the multiple potential coordination modes of the stp ligand and the bipy co-ligand, the products are structurally and topologically diverse with the connectivities of the materials dependent on the ratios of starting materials employed. Single-crystal X-ray diffraction studies show that compound 1 is a three-dimensional coordination polymer, compound 2 consists of infinite one-dimensional zig-zag chains, compound 3 is a discrete trinuclear complex, compound 4 is a discrete mononuclear complex and compound 5 is an ionic solid consisting of both cobalt containing cations and anions. Magnetic studies show that the Co(II) ions in 1 are strongly coupled, while 2, 3 and 5 show insignificant coupling due to larger metal–metal separations. Modelling required the introduction of zero field splitting parameters due to orbital angular momentum contributions in these cases.

A new type of paddle-wheel coordination complex

In the presence of Na(+) ions, the reaction of the ligand 2-hydroxy-1,3-bis-(3-oxo-3-(2-hydroxyphenyl)-propionyl)-benzene, H5L4, with M(AcO)2 salts (M = Mn, Co) gathers the conditions for the assembly of coordination complexes (NBu4)3[M2Na2(H2L4)3] (M = Mn(II) 1 and Co(II) 2), which exhibit a new paddle-wheel structure. The features of this new category of compounds are discussed as well as their magnetic properties and solution behaviour.