Modulated spin dynamics of [Co2] coordination helicates via differential strand composition.

Coordination supramolecular chemistry provides a versatile entry into materials with functionalities of technological relevance at the nanoscale. Here, we describe how two different bis-pyrazolylpyridine ligands (L1 and L2) assemble with Co(II) ions into dinuclear triple-stranded helicates, in turn, encapsulating different anionic guests. These constructs are described as (Cl@[Co2(L1)3])3+, (SiF6@[Co2(L1)(L2)3])2+ and (ClO4@[Co2(L2)3])3+, as established by single-crystal X-ray diffraction. Extensive magnetic and calorimetric measurements, numerical treatments and theoretical calculations reveal that the individual Co(II) centers of these supramolecular entities exhibit field-induced slow relaxation of magnetization, dominated by direct and Raman mechanisms. While the small variations in the spin dynamics are not easily correlated with the evident structural differences among the three species, the specific heat measurements suggest two vibronic pathways of magnetic relaxation: one that would be associated with the host lattice and another linked with the guest.

A supramolecular helicate with two independent Fe(II) switchable centres and a [Fe(anilate)3]3- guest.

A biphenyl-spaced bis-pyrazolylpyridine ligand interacts with ferrous ions to engender a dimetallic helical coordination cage that encapsulates an Fe3+ tris-anilate complex. The host-guest interaction breaks the symmetry of the Fe2+ centers causing a differential spin crossover behavior in them that can be followed in great detail crystallographically.

The template effect of a SiF62- guest drives the formation of a heteroleptic Fe(II) coordination helicate.

The anion SiF62- exerts a strong template effect, driving the exclusive assembly of two different bispyridylpyrazolyl ligands into a triple stranded Fe(II) dinuclear heteroleptic helicate, engendering a new class within the large family of coordination helicates.

Unparalleled selectivity and electronic structure of heterometallic [LnLn'Ln] molecules as 3-qubit quantum gates.

Heterometallic lanthanide [LnLn'] coordination complexes that are accessible thermodynamically are very scarce because the metals of this series have very similar chemical behaviour. Trinuclear systems of this category have not been reported. A coordination chemistry scaffold has been shown to produce molecules of type [LnLn'Ln] of high purity, i.e. exhibiting high metal distribution ability, based on their differences in ionic radius. Through a detailed analysis of density functional theory (DFT) based calculations, we discern the energy contributions that lead to the unparalleled chemical selectivity of this molecular system. Some of the previously reported examples are compared here with the newly prepared member of this exotic list, [Er2Pr(LA)2(LB)2(py)(H2O)2](NO3) (1) (H2LA and H2LB are two ß-diketone ligands). A magnetic analysis extracted from magnetization and calorimetry determinations identifies the necessary attributes for it to act as an addressable, conditional multiqubit spin-based quantum gate. Complementary ab initio calculations confirm the feasibility of these complexes as composite quantum gates, since they present well-isolated ground states with highly anisotropic and distinct g-tensors. The electronic structure of 1 has also been analyzed by EPR. Pulsed experiments have allowed the establishment of the quantum coherence of the transitions within the relevant spin states, as well as the feasibility of a coherent control of these states via nutation experiments.

A ferric guest inside a spin crossover ferrous helicate.

A designed dimetallic Fe(II) helicate made with biphenylene-bridged bispyrazolylpyridine ligands and exhibiting a process of spin crossover at temperatures above ambient is shown to encapsulate an S = 5/2 tris-oxalato Fe(III) ion. The spin relaxation dynamics of this guest are strongly reduced upon encapsulation.

Unravelling of a [High Spin-Low Spin] ↔ [Low Spin-High Spin] Equilibrium in Spin-Crossover Iron(II) Dinuclear Helicates Using Paramagnetic NMR Spectroscopy.

Spin-crossover between high-spin (HS) and low-spin (LS) states of selected transition metal ions in polynuclear and polymeric compounds is behind their use as multistep switchable materials in breakthrough electronic and spintronic devices. We report the first successful attempt to observe the dynamics of a rarely found broken-symmetry spin state in binuclear complexes, which mixes the states [HS-LS] and [LS-HS] on a millisecond timescale. The slow exchange between these two states, which was identified by paramagnetic NMR spectroscopy in solutions of two spin-crossover iron(II) binuclear helicates that are amenable to molecular design, opens a path to double quantum dot cellular automata for information storage and processing.

Piano-Stool Ruthenium(II) Complexes with Delayed Cytotoxic Activity: Origin of the Lag Time.

We have recently reported a series of piano-stool ruthenium(II) complexes of the general formula [RuCl2(η6-arene)(P(1-pyrenyl)R2R3)] showing excellent cytotoxic activities (particularly when R2 = R3 = methyl). In the present study, new members of this family of compounds have been prepared with the objective to investigate the effect of the steric hindrance of a bulky phosphane ligand, namely diisopropyl(1-pyrenyl)phosphane (L), on exchange reactions involving the coordinated halides (X = Cl, I). Two η6-arene rings were used, i.e. η6-methyl benzoate (mba) and η6-p-cymene (p-cym), and four complexes were synthesized, namely [RuCl2(mba)(L)] (1Cl2iPr), [RuI2(mba)(L)] (1I2iPr), [RuCl2(p-cym)(L)] (2Cl2iPr), and [RuI2(p-cym)(L)] (2I2iPr). Unexpectedly, all of the complexes exhibited poor cytotoxic activities after 24 h of incubation with cells, in contrast to the related compounds previously reported. However, it was observed that aged DMSO solutions of 2I2iPr (from 2 to 7 days) exhibited better activities in comparison to freshly prepared solutions and that the activity improved over "aging" time. Thorough studies were therefore performed to uncover the origin of this lag time in the cytotoxicity efficiency. The data achieved clearly demonstrated that compounds 2I2iPr and 2Cl2iPr were undergoing a series of transformation reactions in DMSO (with higher rates for the iodido complex 2I2iPr), ultimately generating cyclometalated species through a mechanism involving DMSO as a coordinated proton abstractor. The cyclometalated complexes detected in solution were subsequently prepared; hence, pure [RuCl(p-cym)(κ2C-diisopropyl(1-pyrenyl)phosphane)] (3CliPr), [RuI(p-cym)(κ2C-diisopropyl(1-pyrenyl)phosphane)] (3IiPr), and [Ru(p-cym)(κS-dmso)(κ2C-diisopropyl(1-pyrenyl)phosphane)]PF6 (3dmsoiPr) were synthesized and fully characterized. Remarkably, 3CliPr, 3IiPr, and 3dmsoiPr are all very efficient cytotoxic agents, exhibiting slightly better activities in comparison to the chlorido noncyclometalated complexes [RuCl2(η6-arene)(P(1-pyrenyl)R2R3)] described in an earlier report. For comparison purposes, the iodido compounds [RuI2(mba)(dimethyl(1-pyrenyl)phosphane)] (1I2Me) and [RuI2(p-cym)(dimethyl(1-pyrenyl)phosphane)] (2I2Me), bearing the less hindered dimethyl(1-pyrenyl)phosphane ligand, have also been prepared. The cytotoxic and chemical behaviors of 1I2Me and 1I2Me were comparable to those of their chlorido counterparts reported previously.

Two [Ln4] molecular rings folded as compact tetrahedra.

The design of photoactive ligands may provide access to multifunctional molecular nanomagnets. We report here the design and synthesis of a new multitopic chelating ligand, 1,2-bis-(5-(N'-(pyridine-2-yl-methylene)-carbohydrazide)-3-methyl-thien-3-yl)-cyclopentene (H2L), bearing a photoswitchable spacer and demonstrate that it undergoes reversible photoisomerization in solution. In the presence of the base NaH, H2L reacts with LnCl3 salts (Ln = Dy, Tb) to form the supramolecular assemblies H2O@[Ln4L4Cl4(H2O)4] (Ln = Dy, 1; Tb, 2). The single crystal X-ray diffraction data of 1 and 2 reveal that both compounds consist of highly symmetric molecular rings efficiently folded through intramolecular weak interactions in the form of tetrahedra. This arrangement imparts a conformation to the photochromic spacer of the ligand which inhibits its photoswitching activity. Despite the low symmetry of the coordination geometry around the Ln ions, the Dy analog exhibits slow relaxation of the magnetization. The relaxation rate under various conditions has been investigated, allowing us to elucidate the mechanisms involved in this relaxation.

A heterometallic [LnLn'Ln] lanthanide complex as a qubit with embedded quantum error correction.

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.

A dissymmetric [Gd2] coordination molecular dimer hosting six addressable 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.

Designed asymmetric coordination helicates with bis-ß-diketonate ligands.

A new bis-(ß-diketone) ligand featuring built-up structural asymmetry yields non-symmetric Fe(iii) and Ga(iii) dinuclear, triple-stranded helicates by design. Their structural properties have been studied, both in solid state and in solution, and compared with their corresponding symmetric analogues. The robustness observed shows the potential of this synthetic strategy to develop non-symmetric helicoidal motifs with specific functional groups.

Controlled Heterometallic Composition in Linear Trinuclear [LnCeLn] Lanthanide Molecular Assemblies.

The combination of two different ß-diketone ligands facilitates the size-controlled assembly of pure heterometallic [LnLn'Ln] linear compounds thanks to two different coordination sites present in the molecular scaffold. [HoCeHo], [ErCeEr], and [YbCeYb] analogues are presented here and are characterized both in the solid state and in solution, demonstrating the selectivity of this unique method to produce heterometallic 4f molecular entities.

Access to indolines from primary phenylethylamines by an unexpected palladium-catalyzed C-H functionalization process.

A new method for the preparation of 2,2-disubstituted indolines from 2-phenylethylamines was developed under Pd catalysis and PhI(OAc)2 as oxidant. Imines derived from 2-pyridinecarboxaldehyde were formed in situ to direct a C-H activation process. The resulting imines were also oxidized to the corresponding amides in the same Pd-catalyzed process to obtain the final indoline as a picolinamide.

Highly Cytotoxic Ruthenium(II)-Arene Complexes from Bulky 1-Pyrenylphosphane Ligands.

In the present study, the potential anti-neoplastic properties of a series of ruthenium half-sandwich complexes of formula [Ru(η6-arene)Cl2(PR1R2(1-pyrenyl))] (η6-arene = p-cymene and R1 = R2 = methyl for 1; η6-arene = methylbenzoate and R1 = R2 = methyl for 2; η6-arene = p-cymene and R1 = R2 = phenyl for 3; η6-arene = methylbenzoate and R1 = R2 = phenyl for 4; η6-arene = p-cymene, R1 = methyl and R2 = phenyl for 5; η6-arene = methylbenzoate, R1 = methyl and R2 = phenyl for 6) have been investigated. The six structurally related organoruthenium(II) compounds have been prepared in good yields and fully characterized; the X-ray structures of three of them, i.e., 1, 2, and 4, were determined. Although the piano-stool compounds contain a large polycyclic aromatic moiety, viz. a 1-pyrenyl group, they do not appear to interact with DNA. However, all the piano-stool complexes show significant cytotoxic properties against five human cell lines, namely, lung adenocarcinoma (A549), melanoma (A375), colorectal adenocarcinoma (SW620), breast adenocarcinoma (MCF7), and nontumorigenic epithelial breast (MCF10A), with IC50 values in the micromolar range for most of them. In addition, the most active compound, i.e., 2, induces a remarkable decrease of cell viability, that is in the nanomolar range, against two human neuroblastoma cell lines, namely, SK-N-BE(2) and CHLA-90. Complexes 1-6 are all capable of inducing apoptosis, but with various degrees of magnitude. Whereas 1, 3, 5, and 6 have no effect on the cell cycle of A375 cells, 2 and 4 can arrest it at the G2/M phase; furthermore, 2 (which is the most efficient compound of the series) also stops the cycle at the S phase, behaving as the well-known anticancer agent cisplatin. Finally, 2 is able to inhibit/reduce the cell migration of neuroblastoma SK-N-BE(2) cells.

Encapsulation of a CrIII Single-Ion Magnet within an FeII Spin-Crossover Supramolecular Host.

Single functional molecules are regarded as future components of nanoscale spintronic devices. Supramolecular coordination chemistry provides unlimited resources to implement multiple functions to individual molecules. A novel coordination [Fe2 ] helicate exhibiting spin-crossover is demonstrated to be ideally suited to encapsulate a [Cr(ox)3 ]3- complex anion (ox=oxalate), unveiling for the first-time single ion slow relaxation of the magnetization for this metal. A possibility of tuning the dynamics of this relaxation as well as the performance of the CrIII center as qubit arises from the observation that metastable high spin FeII centers from the host can be generated by irradiation with green light at low temperature.

Selective Lanthanide Distribution within a Comprehensive Series of Heterometallic [LnPr] Complexes.

The preparation of heterometallic, lanthanide-only complexes is an extremely difficult synthetic challenge. By a ligand-based strategy, a complete isostructural series of dinuclear heterometallic [LnPr] complexes has been synthesized and structurally characterized. The two different coordination sites featured in this molecular entity allow study of the preferences of the praseodymium ion for a specific position depending on the ionic radii of the accompanying lanthanide partner. The purity of each heterometallic moiety has been evaluated in the solid state and in solution by means of crystallographic and spectrometric methods, respectively, revealing the limits of this strategy for ions with similar sizes. DFT calculations have been carried out to support the experimental results, confirming the nature of the site-selective lanthanide distribution. The predictable selectivity of this system has been exploited to assess the magnetic properties of the [DyPr] and [LuPr] derivatives, showing that the origin of the slow dynamics observed in the former arises from the dysprosium ion.

Photoactivation of the Cytotoxic Properties of Platinum(II) Complexes through Ligand Photoswitching.

The development of photoactivatable metal complexes with potential anticancer properties is a topical area of current investigation. Photoactivated chemotherapy using coordination compounds is typically based on photochemical processes occurring at the metal center. In the present study, an innovative approach is applied that takes advantage of the remarkable photochemical properties of diarylethenes. Following a proof-of-concept study with two complexes, namely, C1 and C2, a series of additional platinum(II) complexes from dithienylcyclopentene-based ligands was designed and prepared. Like C1 and C2, these new coordination compounds exhibit two thermally stable, interconvertible photoisomers that display distinct properties. The photochemical behavior of ligands L3-L7 has been analyzed by 1H NMR and UV-vis spectroscopies. Subsequently, the corresponding platinum(II) complexes C3-C7 were synthesized and fully characterized, including by single-crystal X-ray diffraction for some of them. Next, the interaction of each photoisomer (i.e., containing the open or closed ligand) of the metal complexes with DNA was examined thoroughly using various techniques, revealing their distinct DNA-binding modes and affinities, as observed for the earlier compounds C1 and C2. The antiproliferative activity of the two forms of the complexes was then assessed with five cancer cell lines and compared with that of C1 and C2, which supported the use of such diarylethene-based systems for the generation of a new class of potential photochemotherapeutic metallodrugs.

Drastic Effect of the Peptide Sequence on the Copper-Binding Properties of Tripeptides and the Electrochemical Behaviour of Their Copper(II) Complexes.

The binding and electrochemical properties of the complexes CuII -HAH, CuII -HWH, CuII -Ac-HWH, CuII -HHW, and CuII -WHH have been studied by using NMR and UV/Vis spectroscopies, CV, and density functional calculations. The results obtained highlight the importance of the peptidic sequence on the coordination properties and, consequently, on the redox properties of their CuII complexes. For CuII -HAH and CuII -HWH, no cathodic processes are observed up to -1.2 V; that is, the complexes exhibit very high stability towards copper reduction. This behaviour is associated with the formation of very stable square-planar (5,5,6)-membered chelate rings (ATCUN motif), which enclose two deprotonated amides. In contrast, for non-ATCUN CuII -Ac-HWH, CuII -HHW complexes, simulations seem to indicate that only one deprotonated amide is enclosed in the coordination sphere. In these cases, the main electrochemical feature is a reductive irreversible one electron-transfer process from CuII to CuI , accompanied with structural changes of the metal coordination sphere and reprotonation of the amide. Finally, for CuII -WHH, two major species have been detected: one at low pH (<5), with no deprotonated amides, and another one at high pH (>10) with an ATCUN motif, both species coexisting at intermediate pH. The present study shows that the use of CV, using glassy carbon as a working electrode, is an ideal and rapid tool for the determination of the redox properties of CuII metallopeptides.

A Magneto-optical Molecular Device: Interplay of Spin Crossover, Luminescence, Photomagnetism, and Photochromism.

A bis(pyrazolylpyridyl) ligand, L, containing a central photochromic dithienylethene spacer predictably forms a ferrous [Fe2 L3 ]4+ helicate exhibiting spin crossover (SCO). In solution, the compound [Fe2 L3 ](ClO4 )4 (1) preserves the magnetic properties and is fluorescent. The structure of 1 is photo-switchable following the reversible ring closure/opening of the central dithienylethene via irradiation with UV/visible light. This photoisomerization switches on and off some emission bands of 1 and provides a means of externally manipulating the magnetic properties of the assembly.

Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies.

The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL)3 (NO3 )(py)(H2 O)] (1), (Hpy)[CeEr(HL)3 (NO3 )(py)(H2 O)] (2), (Hpy)[CeGd(HL)3 (NO3 )(py)(H2 O)] (3), (Hpy)[PrSm(HL)3 (NO3 )(py)(H2 O)] (4), and (Hpy)2 [LaYb(HL)3 (NO3 )(H2 O)](NO3 ) (5), in which H3 L is 6-(3-oxo-3-(2-hydroxyphenyl)propionyl)pyridine-2-carboxylic acid and py is pyridine, were analyzed experimentally and by using DFT calculations. Complexes 3, 4, and 5 are described here for the first time, and were analyzed by using single-crystal X-ray diffraction and mass spectrometry. The theoretical study was also extended to the [LaCe] and [LaLu] analogues. The results are consistent with a remarkable selectivity of the metal distribution within the molecule in the solid state, enhanced by the size difference between the different ions. This selectivity was reduced in solution, particularly for ions with the most similar radii. This unique entry into 4f-4f'' heterometallic chemistry establishes for the first time the difference between the selectivity in solution and that in the solid state, as a result of changes to the coordination that follow the dissociation of terminal ligands upon dissolution of the complexes.