European research platform IPANEMA at the SOLEIL synchrotron for ancient and historical materials

IPANEMA, a research platform devoted to ancient and historical materials (archaeology, cultural heritage, palaeontology and past environments), is currently being set up at the synchrotron facility SOLEIL (Saint‐Aubin, France; SOLEIL opened to users in January 2008). The new platform is open to French, European and international users. The activities of the platform are centred on two main fields: increased support to synchrotron projects on ancient materials and methodological research. The IPANEMA team currently occupies temporary premises at SOLEIL, but the platform comprises construction of a new building that will comply with conservation and environmental standards and of a hard X‐ray imaging beamline today in its conceptual design phase, named PUMA. Since 2008, the team has supported synchrotron works at SOLEIL and at European synchrotron facilities on a range of topics including pigment degradation in paintings, composition of musical instrument varnishes, and provenancing of medieval archaeological ferrous artefacts. Once the platform is fully operational, user support will primarily take place within medium‐term research projects for `hosted' scientists, PhDs and post‐docs. IPANEMA methodological research is focused on advanced two‐dimensional/three‐dimensional imaging and spectroscopy and statistical image analysis, both optimized for ancient materials.     

Cyclic Polymers by Ring‐Closure Strategies

The preparation of cyclic macromolecules has always represented a challenging task for polymer science, mainly because of difficulties in connecting chain extremities together. Initiated by the pioneering studies of Jacobson and Stockmayer, preparative pathways to cyclic polymers have been considerably improved within the last two decades thanks to the advent of both controlled polymerizations and efficient coupling reactions in organic chemistry. This Review aims to provide a critical up‐to‐date overview and illustrate the considerable efforts that have been made in the past few years to improve the availability of macrocycles for industrial and academic investigations through the use of the ring‐closure approach. Particular attention is paid to methods for the preparation of monocycles over more complex architectures, since the latter are usually derived from the former.     

Luminescent charge-transfer platinum(II) metallacycle

The photophysical and electrochemical properties of a platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan-2,2'-diacetylide (tda), Pt(dbbpy)(tda) [dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine] (1), are compared with two reference compounds, Pt(dbbpy)(C[triple bond]CPh)(2) (2) and Pt(dppp)tda [dppp = 1,3-bis(diphenylphosphino)propane] (3), respectively. The X-ray crystal structure of 1 is reported, which illustrates the nearly perfect square planarity exhibited by this metallacycle. Chromophore 2 possesses low-lying charge-transfer excited states analogous to 1, whereas structure 3 lacks such excited states but features a low-lying platinum-perturbed tda intraligand triplet manifold. In CH(2)Cl(2), 1 exhibits a broad emission centered at 562 nm at ambient temperature, similar to 2, but with a higher photoluminescence quantum yield and longer excited-state lifetime. In both instances, the photoluminescence is consistent with triplet-charge-transfer excited-state parentage. The rigidity imposed by the cyclic diacetylide ligand in 1 leads to a reduction in nonradiative decay, which enhances its room-temperature photophysical properties. By comparison, 3 radiates highly structured tda-localized triplet-state phosphorescence at room temperature. The 77 K emission spectrum of 1 in 4:1 EtOH/MeOH becomes structured and is quantitatively similar to that measured for 3 under the same conditions. Because the 77 K spectra are nearly identical, the emissions are assigned as (3)tda in nature, implying that the charge-transfer states are raised in energy, relative to the (3)tda levels in 1 in the low-temperature glass. Nanosecond transient absorption spectrometry and ultrafast difference spectra were determined for 1-3 in CH(2)Cl(2) and DMF at ambient temperature. In 1 and 2, the major absorption transients are consistent with the one-electron reduced complexes, corroborated by reductive spectroelectrochemical measurements performed at room temperature. As 3 does not possess any charge-transfer character, excitation into the pipi* transitions of the tda ligand generated transient absorptions in the relaxed excited state assigned to the ligand-localized triplet state. In all three cases, the excited-state lifetimes measured by transient absorption are similar to those measured by time-resolved photoluminescence, suggesting that the same excited states giving rise to the photoluminescence are responsible for the absorption transients. ESR spectroscopy of the anions 1- and 2- and reductive spectroelectrochemistry of 1 and 2 revealed a LUMO based largely on the pi* orbital of the dbbpy ligand. Time-dependent density functional theory calculations performed on 1-3 both in vacuum and in a CH(2)Cl(2) continuum revealed the molecular orbitals, energies, dipole moments, and oscillator strengths for the various electronic transitions in these molecules. A DeltaSCF-method-derived shift applied to the calculated transition energies in the solvent continuum yielded good agreement between theory and experiment for each molecule in this study.     

Magnetic structures of the M2TbF6 (M=Li, K, Rb) fluorides: A complex behavior resulting from frustration

Neutron powder diffraction has been performed on Li₂TbF₆, K₂TbF₆ and Rb₂TbF₆ fluoroterbates. Incommensurate long-range magnetic order is observed below T_N=2.02, 1.60 and 2.07 K. The square-modulating of the magnetic structures can be correlated with the geometric frustration induced by the pseudo-hexagonal packing of the [TbF₆]²⁻ chains in these hexafluorides. This frustration and the magnetic interactions are discussed on the basis of experimental data and topological considerations. The magnetic structures encountered in this series, and the particular thermal evolution of the Li₂TbF₆ magnetic structure may result from the competition between the magnetic interactions taking place in the chains and the magnetic interactions coupling the chains.     

On the Degree of Caustics by Reflection

Given a point S ∈ ?²: = ?²(?) and an irreducible algebraic curve 𝒞 of ?² (with any type of singularities), we consider the lines ? _m obtained by reflection of the lines (S m) on 𝒞 (for m ∈ 𝒞). The caustic by reflection Σ _S (𝒞) is classically defined as the Zariski closure of the envelope of the reflected lines ? _m . We identify this caustic with the Zariski closure of Φ(𝒞), where Φ is some rational map. We use this approach to give general and explicit formulas for the degree (with multiplicity) of caustics by reflection. Our formulas are expressed in terms of intersection numbers of the initial curve 𝒞 (or of its branches). Our method is based on a fundamental lemma for rational map thanks to the notion of Φ-polar and on the computation of intersection numbers. In particular, we use precise estimates related to the intersection numbers of 𝒞 with its polar at any point and to the intersection numbers of 𝒞 with its Hessian curve. These computations are linked with generalized Plücker formulas for the class and for the number of inflection points of 𝒞.     

Multiple imputation in principal component analysis

The available methods to handle missing values in principal component analysis only provide point estimates of the parameters (axes and components) and estimates of the missing values. To take into account the variability due to missing values a multiple imputation method is proposed. First a method to generate multiple imputed data sets from a principal component analysis model is defined. Then, two ways to visualize the uncertainty due to missing values onto the principal component analysis results are described. The first one consists in projecting the imputed data sets onto a reference configuration as supplementary elements to assess the stability of the individuals (respectively of the variables). The second one consists in performing a principal component analysis on each imputed data set and fitting each obtained configuration onto the reference one with Procrustes rotation. The latter strategy allows to assess the variability of the principal component analysis parameters induced by the missing values. The methodology is then evaluated from a real data set.     

Ultrafast energy migration in platinum(II) diimine complexes bearing pyrenylacetylide chromophores

The ultrafast excited-state dynamics of three structurally related platinum(II) complexes has been investigated using femtosecond transient absorption spectrometry in 2-methyltetrahydrofuran (MTHF). Previous work has shown that Pt(dbbpy)(C[triple bond]C-Ph)2 (dbbpy is 4,4'-di(tert-butyl)-2,2'-bipyridine and C[triple bond]C-Ph is ethynylbenzene) has a lowest metal-to-ligand charge transfer (3MLCT) excited state, while the multichromophoric Pt(dbbpy)(C[triple bond]C-pyrene)2 (CC-pyrene is 1-ethynylpyrene) contains the MLCT state, but possesses a lowest intraligand (3IL) excited state localized on one of the CC-pyrenyl units (Pomestchenko, I. E.; Luman, C. R.; Hissler, M.; Ziessel, R.; Castellano, F. N. Inorg. Chem. 2003, 42, 1394-96). trans-Pt(PBu3)2(C[triple bond]C-pyrene)2 serves as a model system that provides a good representation of the CC-pyrene-localized 3IL state in a Pt(II) complex lacking the MLCT excited state. Following 400 nm excitation, the formation of the 3MLCT excited state in Pt(dbbpy)(C[triple bond]C-Ph)2 is complete within 200 +/- 40 fs, and intersystem crossing to the 3IL excited state in trans-Pt(PBu3)2(C[triple bond]C-pyrene)2 occurs with a time constant of 5.4 +/- 0.2 ps. Selective excitation into the low-energy MLCT bands in Pt(dbbpy)(C[triple bond]C-pyrene)2 (lambda(ex) = 480 nm) leads to the formation of the 3IL excited state in 240 +/- 40 fs, suggesting ultrafast wire-like energy migration in this molecule. The kinetic data suggest that the presence of the MLCT states in Pt(dbbpy)(C[triple bond]C-pyrene)2 markedly accelerates the formation of the triplet state of the pendant pyrenylacetylide ligand. In essence, the triplet sensitization process is kinetically faster than pure intersystem crossing in trans-Pt(PBu3)2(CC-pyrene)2 as well as vibrational relaxation in the MLCT excited state of Pt(dbbpy)(C[triple bond]C-Ph)2. These results are potentially important for the design of chromophores intended to reach their lowest excited state on subpicosecond time scales and advocate the likelihood of wire-like behavior in triplet-triplet energy transfer.