The KidamySyn project is built on the collaboration of three teams (Nantes, Rennes, Le Mans) and plans to achieve the first total synthesis of Kidamycin, a member of the Pluramycins family. This project submitted in 2013 has been selected on the additional list and received very good appreciations from the evaluation committee. This situation convinced the constituted consortium to resubmit the proposal in a revised form with a better distribution of tasks between the different partners and additional informations about the few remarks emphasised by the referees. The pluramycins display a 4H-anthra[1,2-b]pyran-4,7,12-trione structure with attached C-glycoside moieties (D-angolosamine and L-vancosamine) and a remote epoxide or unsaturated lateral chain. Their core structure with four contiguous rings, one of which being angularly disposed, is clearly reminiscent of the angucycline class of natural compounds. Besides their remarkable structure, many members of the pluramycin family have promising biological activities, making it a particularly attractive target for organic chemists. Following our common experience in the chemistry of angucyclines and in the development of innovative synthetic methodologies, our project aims to design and to realise the total synthesis of kidamycin following a convergent strategy that should be efficiently transposed in a second phase to the synthesis of analogues and pluramycin-related molecules with potential enhanced activities. We will first focus our attention on the synthesis of kidamycin aglycone named kidamycinone. The pluramycinone skeleton will be elaborated in a highly convergent manner via B-ring construction by Diels-Alder cycloadditions involving novel dienes already possessing the lateral chains and juglone. This first task, based in part on the results already obtained in our laboratory, should enable to strengthen the viability of our synthetic plan towards the kidamycin. The main goal of the project, the synthesis of kidamycin itself, will start by the preparation of the dienophile partner with its two C-glycoside appendages and its subsequent reaction with appropriate diene. Recent literature reports mention the difficulties encountered in installing the two unit sugars by direct C-glycosidation with the appropriate stereoconfiguration mainly for the L-vancosamine link. We therefore designed a new stereocontrolled approach based on a direct C-glycosidation with D-angolosamine followed by the critical introduction of L-vancosamine unit by univocal transformation of the corresponding glycal. Finally, the Diels-Alder strategy developed for kidamycinone will be applied to couple the two key fragments to afford kidamycin after a limited number of further functional transformations. This convergent route, associated with the potential structural diversity of the dienyl building blocks, would enable access to other pluramycin-related compounds and related simplified derivatives. Encouraging preliminary results indicate that the challenging objectives of this project, the total synthesis of kidamycin and the development of innovating synthetic strategies, should be reasonably achieved under the proposed schedule.

Ultrafast light excitation is expected to trigger new states in solids, which are not accessible by varying the pressure, temperature, or doping in standard thermodynamic equilibrium conditions. Ultrafast terahertz (THz) spectroscopy has been blooming for the last 20 years. Developments of new intense THz sources provide the tools to trig not only the linear response but also the nonlinear response of matter offering new perspectives in exploring extreme matter behavior at the picoseconds timescale. In solid state physics, different degrees of freedom have been addressed dynamically by driving electrons, phonons or spins well out-of-equilibrium with ultrashort THz pulses. The EPHONO project is focus on fundamental aspects of the light induced ultrafast lattice dynamics in condensed matter. It aims at unraveling the complexity of coherent phonon-phonon interactions with high THz field at the sub-picoseconds timescales. In the EPHONO project, I will apply the nonlinear phononics framework in order to explore the optical phonons ultrafast dynamics into the nonlinear regime. As optical phonons are mediating matter properties (the “soft mode” in phase transition material, the ferroelectric mode in multiferroics material to name a few), it is crucial to develop experimental and theoretical methods to study, explain and predict the excitation pathways in this extreme nonlinear regime. To achieve this, I propose to tackle this problem in two connected ways by experimental and theoretical investigations. The first one will be dedicated to the development of state-of-art nonlinear ultrafast THz spectroscopy and the second one to ab-initio calculations within the Density Functional Theory. Within this context, the EPHONO project will be at the core of developments both experimentally (2D THz spectroscopy) and theoretically (ab-initio calculations). The main idea of the experimental approach is based on the fact that “regular” ultrafast nonlinear spectroscopy in the THz range is not enough to fully understand the ultrafast lattice dynamics: single-pulse excitation does not fully unravel the complexity of phonon-phonon interaction. That is why, extending the experimental technique to multidimensional ultrafast THz spectroscopy associated to a THz frequency tunability, will allow distinguishing the dominant optical phonon mode excitation pathway. More precisely, this technique is based on using a multiple pump pulses sequence, which allows decoupling the excitation frequency to the detected frequency by looking at their correlation in the frequency domain. This powerful method can help to unravel the different coupling pathways leading to the excitation of one specific optical phonon mode. It can be implemented in two ways: either by measuring the optical properties change with a delayed optical probe (2D THz-Raman) or by measuring the total transmitted THz electric field by an electro-optic sampling technique (2D THz Spectroscopy). The experimental aspects of the project EPHONO will be supported by “in-house” theoretical approach with ab-initio calculations (Density Functional Theory) within the framework of the local density approximation with Spin-orbit coupling included. The purpose of these calculations is to understand the obtained experimental results in the case of a Bi2Te3 nanofilm excited with a strong THz pulse. The aim is to be able to have a quantitative comparison between experimental and high end first principles calculations. The strategy will be focused on continuing investigating topological insulator like nanofilm of Bi2Te3. This type of material possesses strong anharmonicities and, thus, makes them ideal for studying nonlinear phononics. In a second step of this project, other materials will be studied such as multiferroic and ferroelectric materials in which another degree of complexity exists. Applying the multidimensional spectroscopy will provide new insights in this multi-orders material.

The advent of femtosecond lasers in the field of solid state physics has been at the origin of many discoveries. For instance, in the field of magnetism it was possible in the last decade to understand how femtosecond optical demagnetization can probe the exchange interaction in ferromagnetic metals. The core of the UltrAMOX proposal is to explore how optically generated ultrafast acoustic waves interact with the magnetization of a thin film, and vice versa, how femtosecond demagnetization can lead to longitudinal and shear acoustic waves excitation from the release of magnetostrictive stresses. The later relevant physical framework is known as direct magnetostriction, which is the property of ferromagnetic materials that causes them to change their shape or dimensions during the process of magnetization or demagnetization. The reverse phenomenon appears when an applied external stress modifies statically or dynamically the magnetization configuration of a ferromagnet. A number of novel interesting physical phenomena can be expected to arise when an ultrafast acoustic pulse, excited through absorption of a femtosecond laser pulse at a photoacoustic transducer, is injected through a ferromagnetic sample (for instance a thin ferromagnetic film or a nanostructured array of ferromagnets). Under some specific conditions that have to be clearly identified, this generic idea termed "acousto- spintronics" could allow for ultrafast magnetization manipulation. Reversely, ultrafast demagnetization of magnetostrictive ferromagnets from femtosecond laser pulses is expected to release ultrafast acoustic pulses that carry out crucial information on the onset of spin-lattice coupling. The UltrAMOX project is a three-year fundamental and experimental project in which we aim to address the phenomena of direct and inverse laser mediated ultrafast magnetostriction in ferromagnets relevant to spintronics. We propose to merge picosecond ultrasonics where femtosecond lasers are used to excite ultrafast acoustic pulses, with femtomagnetism and spintronics. The goals of UltrAMOX project are twofold and can be listed as following: 1) Direct ultrafast magnetostriction: Investigation of the generation of THz longitudinal and shear acoustic pulses through laser mediated release of magnetostrictive stresses in ferromagnetic compounds. 2) Inverse ultrafast magnetostriction: Investigation of ultrafast interaction of laser generated ultrasonic pulses with spins and magnons in hybrid metal/ferromagnet multilayer structures.

The goal of the ObNAREM project is to make permanent magnets from hetero-nanostructures consolidated from magnetically oxides. The elaborated nanomaterials are dense assemblies of nanocrystallites of ferri and antiferromagnetic oxides of transition metals, quite cheap, initially prepared in a solution, and exhibit a high exchange anisotropy at the interface. The chemical composition and the nanostructure of the nanocomposites before and after consolidation are major adjustment parameters the definition of which will be guided by ab initio modeling and multiscale Monte Carlo calculations, compared to local and global magnetic measurements. These magnets without rare earths should find wide use in the automotive industry for concrete applications for both passenger cars accessories as for performance and efficiency of electrical engines. The use of rare earths in magnets is at the same time a strategic, economical, environmental, and technological problem. This project aims at remediating those issues by bringing together several skills in materials science: nanochemistry, nanopowder metallurgy, magnetism and numerical modeling of confined systems. Sizeable quantities of matter and a prototype electrical engine will be produced in order to characterize in a realistic environment the temperature dependence of the properties of the new magnets, which are expected to exhibit performances close to the ones of present devices, with a better temperature dependence.

Since a few years, the perovskite solar cells (PSCs) have emerged as a new technology for next-generation photovoltaics. These materials, as exemplified by the archetypal methyl-ammonium lead tri-iodide (CH3NH3)PbI3 (MAPI), have several key advantages: PSCs can be prepared using solution processing at temperature not exceeding 150°C, and their power conversion efficiencies (PCE) reach over 22%. However, PSCs have two main drawbacks: they contain the toxic lead element, and they exhibit chemical instabilities to moisture, oxygen, light, etc. In this context, the central goal of the MORELESS project is to develop new materials belonging to the family of halide perovskites, suitable for light absorption in PV devices and offering improved stability (“MORE stable” than MAPI) while alleviating the most troubling issue of toxicity (“LESS lead” than MAPI). MORELESS will implement two different strategies. The first strategy consists in the search for lead deficient HPs materials (d-HPs). This new type of hybrid perovskites, (A,A’)1+xPb1-xI3-x (A, A’, organic monocations), discovered recently by the PI, contains less lead while keeping a 3D architecture, is more stable than MAPI and offers increased flexibility of its chemical composition. We propose to focus on this new type of hybrid perovskite by preparing new materials through substitutions on the A, A’, Pb and I sites. MORELESS also aims at discovering new kinds of d-HPs materials. The second strategy seeks for lead-free materials based on iodobismuthate or iodoantimonate networks. These materials are known to be stable and easily prepared as thin films. While non-perovskite compounds have been mainly used for PSCs applications, we propose to focus on 1D and 2D perovskite networks (corner-sharing octahedra) based materials. The next targets will be stabilization of 3D perovskite NMI3 (M= Bi3+/Sb3+), using neutral molecule N, consistently with recent predictions, as well as monovalent cation such as Ag+ in order to stabilize bismuth(antimony)-rich M3+/Ag+ perovskite networks. Once interesting materials will be obtained and characterized (X-ray, NMR, and others), thin films will be prepared to afford well-crystallized, fully covering, efficient light absorbing and adherent thin films. These layers will be characterized by XRD, SEM, EDX, AFM and XPS. Then the PSCs will be prepared and the cell performances determined for the various new perovskites (e.g., J-V curve measurements and impedance spectroscopy). For the best materials, other full studies will be carried out, particularly the aging of the layers will be followed by several techniques. First principles calculations and modeling will be performed both to support the interpretation of available experimental findings, including NMR data, and provide guidance to determine the choice of the next synthetic targets. Available structural data will allow investigation of electronic and optical properties in relation with experimental outcomes and DFT methods will provide complementary insight for foreseen atomic substitutions. MORELESS is a collaborative project between partners having experience in the field of HPs and a strong expertise in complementary fields that are essential for successful outcome. This multidisciplinary project includes chemistry of materials (task 1), preparation and characterizations of PSCs (task 2) and modeling (task 3). At Moltech-Anjou (Angers, partner 1), the design, and the preparation of materials as well as X-ray characterizations will be assumed by N. Mercier, the coordinator of the project. At the IMMM institute (Le Mans, partner 2), the solid state NMR characterization of materials will be performed by J. Dittmer. In the MPOE-IRCP group of T. Pauporté (Chimie ParisTech, partner 3), material shaping, notably the electrical and optical characterizations and solar cell measurements and aging issue will be carried out. At ISCR (Partner 4) C. Katan will coordinate the theoretical work.