Coordination chemistry in supercritical fluids: from post-synthetic modifications to the synthesis of functional networks – CoordinSCFs

This project proposes to combine the versatilities of coordination chemistry and supercritical fluids (SCFs) for the development of innovative strategies toward the synthesis of molecule-based functional coordination polymers (CPs). Focusing on metal/pyrazine-based systems, the first objectives using SCFs will be the synthesis of new 2D CPs as well as the post-synthetic modifications of known, or newly prepared, 2D CPs in order to optimize their physical properties. This approach has also the potential to lead to a new method for exfoliation of these 2D CPs, which remains essential for future applications in spintronics. In parallel, the design of multifunctional 3D CPs, not accessible from conventional solution chemistry, will be explored bridging metal/pyrazine layers by selected pillars of different lengths, magnetic and redox activity. This strategy aims to design new porous, magnetic, and conducting materials with a tunable and selective CO2 and gas adsorption properties. For these two work-packages, we will use supercritical CO2 and NH3, the latter being quasi-unused so far for coordination chemistry. The unexplored frontier between coordination chemistry and supercritical fluids offers unprecedented opportunities to easily and efficiently synthesize a new generation of (i) optimized, intercalated and exfoliated 2D CPs; as well as (ii) multifunctional 3D CPs. To reach our objectives, this project gathers 3 partners: (i) the M3 team of CRPP, expert in the synthesis and characterizations of pyrazine-based networks, (ii) the supercritical fluids group of ICMCB, expert in SCFs technology and (iii) the MACSE team of the ISCR of Rennes for its experience in the synthesis of functional pillars.