Philippe Guionneau

Bio: Philippe Guionneau is an academic researcher from Centre national de la recherche scientifique. The author has contributed to research in topics: Spin crossover & Crystal structure. The author has an hindex of 39, co-authored 177 publications receiving 5987 citations. Previous affiliations of Philippe Guionneau include University of Bordeaux.

Superconducting and Semiconducting Magnetic Charge Transfer Salts: (BEDT-TTF)4AFe(C2O4)3.cntdot.C6H5CN (A = H2O, K, NH4)

Abstract: We have shown that the hexagonal layer motif [AM{sup III}(C{sub 2} O{sub 4}){sub 3}]{sup n-} containing bridging oxalate groups, which has been shown to form a wide variety of compounds with electronically inactive counter-cations having unusual cooperative magnetic properties, can also stabilize lattices containing the organic {pi}-donor BEDT-TTF. In the compounds whose structures we describe here, (BEDT-TTF){sub 4}AFe(C{sub 2}O{sub 4}){sub 3}.C{sub 6}H{sub 5} CN (A = H{sub 2}O, K, NH{sub 4}), the lattice is stabilized by C{sub 6} H{sub 5}CN molecules included in the hexagonal cavities. The packing of the BEDT-TTF in the A = K, NH{sub 4} phases is of a type not previously observed with spin-paired (BEDT-TTF){sub 2}{sup 2+} separated by closed shell (BEDT-TTF){sup 0}, while that in the superconductor is of {Beta}{double_prime} type. Both the superconducting A = H{sub 2}O and semiconducting A = K, NH{sub 4} phases contain high spin 3d{sup 5} Fe{sup III} with only very weak exchange interaction between them. Additional low temperature and high magnetic field experiments (e.g., of Schubnikov-de Haas oscillatory magnetoresistance) will be needed to delineate the Fermi surface in the superconductor. 36 refs., 11 figs., 4 tabs.

Towards spin crossover applications

Abstract: In this chapter we attempt to review the potential for the application of the spin crossover (SCO) phenomenon in various domains, such as molecular electronics, data storage, display devices. It is evident that SCO properties, such as room-temperature working range, chemical stability, low addressing power, short addressing time, full reversibility, are of promising value in the context of the stringent limits necessary in the future development of information technology, due to the unceasing miniaturization of the components. Of course, many requirements must be fulfilled before any use in a genuine device becomes feasible. Some of these are emphasized and discussed here. Additionally, this review reports recent progress in non-linear optics and photomagnetism of SCO materials.

Structural aspects of spin crossover. Example of the [FeIILn(NCS)2] complexes

Abstract: The interplay between the spin crossover and the structural properties of the complexes in the solid state is still under investigation. In particular the following questions may be asked. What are the structural modifications of the metal coordination sphere at the spin crossover? How are the dimensions and the symmetry of the crystallographic unit cell affected by the spin crossover? Conversely, how may structural properties influence the spin crossover behavior? Do intramolecular parameters account for the features of the spin crossover? What are the relevant characteristics of the crystal packing for the cooperativity? Do the above questions have general answers that can be used for all the spin crossover compounds? This contribution tries to give answers to these questions. The discussion is based on a large structural data set provided in the literature for the six-coordinated iron(II) mononuclear complexes of general formula [FeL n (NCS) 2 ]. The effects of temperature, light and pressure on the X-ray diffraction crystal structures are reviewed. The structural modifications due to the spin crossover are first estimated, these include the expansion and the distortion of the FeN 6 octahedron, the isotropic and the anisotropic changes of the unit cell. The influence of the structural properties on the features of the spin crossover is then discussed. For example, intramolecular properties such as Fe-N bond lengths are in general not relevant to account for the spin crossover features. In contrast, hydrogen bonds play a paramount role in the propagation of the spin conversion throughout the crystal lattice.

A guideline to the design of molecular-based materials with long-lived photomagnetic lifetimes.

Abstract: Materials presenting a stable and reversible switch of physical properties in the solid state are of major interest either for fundamental interests or potential industrial applications. In this context, the design of metal complexes showing a light-induced crossover from one spin state to another, leading to a major change of magnetic and optical properties, is probably one of the most appealing challenges. The so-denoted spin-crossover materials undergo, in some cases, a reversible photoswitch between two magnetic states, but, unfortunately, lifetimes of the photomagnetic states for compounds known so far are long enough only at low temperatures; this prohibits any applications. We have measured and collected the temperatures above which the photomagnetic effect disappears for more than sixty spin-crossover compounds. On the basis of this large data base, a correlation between the nature of the coordination sphere of the metal and the photomagnetic lifetime can be drawn. Such correlation allows us to propose here a general guideline for the rational design of materials with long-lived photomagnetic lifetimes. This result clearly opens the way towards room-temperature photonic materials, based on the spin-crossover phenomenon, which will be of great interest for future communication devices.

Structure validation in chemical crystallography

Abstract: Automated structure validation was introduced in chemical crystallography about 12 years ago as a tool to assist practitioners with the exponential growth in crystal structure analyses. Validation has since evolved into an easy-to-use checkCIF/PLATON web-based IUCr service. The result of a crystal structure determination has to be supplied as a CIF-formatted computer-readable file. The checking software tests the data in the CIF for completeness, quality and consistency. In addition, the reported structure is checked for incomplete analysis, errors in the analysis and relevant issues to be verified. A validation report is generated in the form of a list of ALERTS on the issues to be corrected, checked or commented on. Structure validation has largely eliminated obvious problems with structure reports published in IUCr journals, such as refinement in a space group of too low symmetry. This paper reports on the current status of structure validation and possible future extensions.

Single-crystal structure validation with the program PLATON

Abstract: The results of a single-crystal structure determination when in CIF format can now be validated routinely by automatic procedures. In this way, many errors in published papers can be avoided. The validation software generates a set of ALERTS detailing issues to be addressed by the experimenter, author, referee and publication journal. Validation was pioneered by the IUCr journal Acta Crystallographica Section C and is currently standard procedure for structures submitted for publication in all IUCr journals. The implementation of validation procedures by other journals is in progress. This paper describes the concepts of validation and the classes of checks that are carried out by the program PLATON as part of the IUCr checkCIF facility. PLATON validation can be run at any stage of the structure refinement, independent of the structure determination package used, and is recommended for use as a routine tool during or at least at the completion of every structure determination. Two examples are discussed where proper validation procedures could have avoided the publication of incorrect structures that had serious consequences for the chemistry involved.

Phd by thesis

Abstract: Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These