• A Synthetic and Mechanistic Investigation of the Chromium Tricarbonyl-Mediated Masamune–Bergman Cyclization. Direct Observation of a Ground-State Triplet p-Benzyne Biradical
    K.E.O. Ylijoki, S. Lavy, A. Fretzen, E.P. Kndig, T. Berclaz, G. Bernardinelli and C. Besnard
    Organometallics, 31 (15) (2012), p5396-5404
    DOI:10.1021/om300427j | unige:22151 | Abstract | Article HTML | Article PDF
A new room-temperature chromium tricarbonyl-mediated cycloaromatization of enediynes is reported. The reaction occurs with both cyclic and acyclic enediynes in the presence of [Cr(CO)36-naphthalene)] and both a coordinating solvent and a hydrogen atom source, providing chromium–arene complexes in reasonable yield and good diastereocontrol. The mechanism of the reaction has been probed through DFT computational and spectroscopic methods. These studies suggest that direct C1–C6 bond formation from an η6-enediyne complex is the lowest-energy path, forming a metal-bound p-benzyne biradical. NMR spectroscopy suggests that enediyne alkene coordination occurs in preference to alkyne coordination, forming a THF-stabilized olefin intermediate; subsequent alkyne coordination leads to cyclization. While biradical quenching occurs rapidly and primarily via the singlet biradical, the triplet state biradical is detectable by EPR spectroscopy, suggesting intersystem crossing to a triplet ground state.
  • Lanthanide-mediated triangular cationic assemblies: structural and physico-chemical properties
    S. Zebret, N. Dupont, C. Besnard, G. Bernardinelli and J. Hamacek
    Dalton Transactions, 41 (16) (2012), p4817-4824
    DOI:10.1039/c2dt12227h | unige:20257 | Abstract | Article HTML | Article PDF
This contribution investigates LnIII complexes formed with a small ditopic ligand, L1, and their structural, thermodynamic and photophysical properties. The spectrophotometric and NMR titrations evidence the triangular assemblies [Ln3(L1-H)3]6+ at stoichiometric conditions and their properties are discussed in relation to L2-containing analogues. In addition, the dinuclear species, [Ln2(L1-H)]5+, is observed with an excess of metal.
  • Unsymmetrical Tripodal Ligand for Lanthanide Complexation: Structural, Thermodynamic, and Photophysical Studies
    B. El Aroussi, N. Dupont, G. Bernardinelli and J. Hamacek
    Inorganic Chemistry, 49 (2) (2010), p606-615
    DOI:10.1021/ic901757u | unige:5248 | Abstract | Article HTML | Article PDF
Two tridentate and one bidentate binding strands have been anchored on a carbon atom to provide a new unsymmetrical tripodal ligand L for Ln(III) coordination. The ligand itself adopts a single conformation in solution stabilized by intramolecular hydrogen bonds evidenced in the solid state. The reaction of L with trivalent lanthanides provides different coordination complexes depending on the metal/ligand ratio. The speciation studies with selected lanthanides were performed in solution by means of NMR, ESMS, and spectrophotometric titrations. Differences in coordination properties along the lanthanide series were evidenced and may be associated with the changes in the ionic size. However, thermodynamic stability constants for the species of the same stoichiometry do not significantly vary. In addition, the structure of the dinuclear complex [Eu2L2]6+ has been elucidated in the solid state, where the complex crystallizes predominantly as an M-isomer. The crystal structure shows the coordination of two different ligands to each europium cation through tridentate strands, and the europium nine-coordinate sphere is completed with three solvent molecules. Finally, the results of photophysical investigations of [Eu2L2]6+ are in close agreement with the structural parameters determined by crystallography.
Triangular luminescent box: Self-assembly of a new multidentate receptor with europium cations results in the formation of trinuclear discrete complexes. X-ray crystallography shows that nine-coordinate cations are linked by ligands to provide a triangular complex in the solid state and in solution. Despite the coordinated solvent molecules, this topologically unusual complex exhibits remarkable luminescent properties.
  • Towards inert and pre-organized d-block-containing receptors for trivalent lanthanides: The synthesis and characterization of triple-helical monometallic OsII and bimetallic OsII-LnIII complexes
    T. Riis-Johannessen, N. Dupont, G. Canard, G. Bernardinelli, A. Hauser and C. Piguet
    Dalton Transactions, 28 (2008), p3661-3677
    DOI:10.1039/b718885d | unige:3572 | Abstract | Article HTML | Article PDF

The mononuclear OsII complex [Os( L1)3](PF6)2 ( L1 = 5-methyl(1-methylbenzimidazol-2-yl)pyridine) is an obvious candidate for the design of an inert d-block-based tripodal receptor capable of binding and photosensitizing trivalent lanthanides (LnIII). It has thus been prepared and its two enantiomeric meridional (Δ-mer and Λ-mer) and facial (rac-fac) isomers have been separated by ion-exchange chromatography. The optical isomers have been characterized by CD spectroscopy and assignments of absolute configuration confirmed by an X-ray crystallographic study of Λ-mer-[Os( L1)3](PF6)2·1.5MeCN (monoclinic, P21, Z = 4). Comparison of the latter structure with that of racemic fac-[Os( L1)3](PF6)2 (monoclinic, C2/c, Z = 8) and [Os(bipy)3](PF6)2 (where bipy = 2,2' -bipyridine) shows minimal structural variations, but differences are observed in the photophysical and electrochemical properties of the respective compounds. Luminescence emissions from OsII complexes of L1 are typically lower in energy, with shorter lifetimes and lower quantum yields than their bipy analogues, whilst metal-centred oxidation processes are more facile due to the enhanced π-donor ability of L1. The key relationships between these parameters are discussed. Finally, though challenged by (i) the low reactivity of many osmium precursors and (ii) the irreversible formation of competing side products, the synthesis and purification of the heterobimetallic triple-stranded helicate HHH-[OsLu( L2)3](CF3SO3)5 has been realised, in which L2 is a segmental ligand containing the same bidentate unit as that found in L1 further connected to a tridentate binding site adapted for complexing LnIII. Its solid-state structure has been established by X-ray crystallography (triclinic, P1-, Z = 2).
  • Tuning the Decay Time of Lanthanide-Based Near Infrared Luminescence from Micro- to Milliseconds through d->f Energy Transfer in Discrete Heterobimetallic Complexes
    S. Torelli, D. Imbert, M. Cantuel, G. Bernardinelli, S. Delahaye, A. Hauser, J.-C.G. Bnzli and C. Piguet
    Chemistry - A European Journal, 11 (11) (2005), p3228-3242
    DOI:10.1002/chem.200401158 | unige:3273 | Abstract | Article HTML | Article PDF
Inert and optically active pseudo-octahedral CrIIIN6 and RuIIN6 chromophores have been incorporated by self-assembly into heterobimetallic triple-stranded helicates HHH-[CrLnL3]6+ and HHH-[RuLnL3]5+. The crystal structures of [CrLnL3](CF3SO3)6 (Ln=Nd, Eu, Yb, Lu) and [RuLnL3](CF3SO3)5 (Ln=Eu, Lu) demonstrate that the helical structure can accommodate metal ions of different sizes, without sizeable change in the intermetallic MLn distances. These systems are ideally suited for unravelling the molecular factors affecting the intermetallic nd→4f communication. Visible irradiation of the CrIIIN6 and RuIIN6 chromophores in HHH-[MLnL3]5/6+ (Ln=Nd, Yb, Er; M=Cr, Ru) eventually produces lanthanide-based near infrared (NIR) emission, after directional energy migration within the complexes. Depending on the kinetic regime associated with each specific d-f pair, the NIR luminescence decay times can be tuned from micro- to milliseconds. The origin of this effect, together with its rational control for programming optical functions in discrete heterobimetallic entities, are discussed.
Unsymmetrical substituted bidentate benzimidazol-2-ylpyridine ligands L2 and L3 react with [Ru(dmso)4Cl2] in ethanol to give statistical 1:3 mixtures of fac-[Ru(Li)3]2+ and mer-[Ru(Li)3]2+ (i=2, 3; ΔGΘisomerisation=-2.7 kJ mol-1). In more polar solvents (acetonitrile, methanol), the free energy of the facial ↔ meridional isomerisation process favours mer-[Ru(Li)3]2+, which is the only isomer observed in solution at the equilibrium (ΔGΘisomerisation≤-11.4 kJ mol-1). Since the latter process takes several days for [Ru(L2)3]2+, fac-[Ru(L2)3]2+ and mer-[Ru(L2)3]2+ have been separated by chromatography, but the 28-fold increase in velocity observed for [Ru(L3)3]2+ provides only mer-[Ru(L3)3](ClO4)2 after chromatography (RuC60H51N9O8Cl2, monoclinic, P21/n, Z=4). The facial isomer can be stabilised when an appended tridentate binding unit, connected at the 5-position of the benzimidazol-2-ylpyridine unit in ligand L1, interacts with nine-coordinate lanthanides(III). The free energy of the facial↔meridional isomerisation is reversed (ΔGΘisomerisation≥11.4 kJ mol-1), and the Ru — N bonds are labile enough to allow the quantitative thermodynamic self-assembly of HHH-[RuLu(L1)3]5+ within hours ([RuLu(L1)3](CF3SO3)4.5Cl0.5(CH3OH)2.5: RuLuC106H109Cl0.5N21O19S4.5F13.5, triclinic, P, Z=2). Electrochemical and photophysical studies show that the benzimidazol-2-ylpyridine units in L1-L3 display similar π-acceptor properties to, but stronger π-donor properties than, those found in 2,2'-bipyridine. This shifts the intraligand π→π* and the MLCT transitions toward lower energies in the pseudo-octahedral [Ru(Li)3]2+ (i=2, 3) chromophores. The concomitant short lifetime of the 3MLCT excited state points to efficient, thermally activated quenching via low-energy Ru-centred d-d states, a limitation which is partially overcome by mechanical coupling in HHH-[RuLu(L1)3]5+.



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