Metallo-supramolecular polymers with photoredox activities: characterization and application

1 D Coordination polymers have attracted a considerable interest because of the great versatility of their fabrication using a simple self-assembly process, especially those incorporating metal ion in a 2,2’:6’,2’’ terpyridine bridging ligand, that allows linear geometry. In that field we propose to study new structures based on some original ditopic ligands bearing two different coordination sites: square planar and octahedral, thus allowing access to well organized bi-metallic coordination polymers (Figure 1). In particular the coordination of Cu+ (tetravalent) in a phenanthroline like ligand could offer applications in conversion and storage of solar energy. During the master intership, the photophysical and electrochemical properties of the building blocks (i.e. [Cu(phen)2]+ and [M(tpy)2] (M= Zn(II), Cr(III) or Co(III)) will first be studied in solution. Then the properties of the coordination polymers will be investigated in solution and after deposition as thin film on electrode. For a Cu/Zn alternated structure a high emissive structure is expected whereas the Co(III) or Cr(III) would allow photoinduced electron transfer process.

Related Publications:
  • New functional polymers and materials based on 2,2’:6’,2’’-terpyridine metal complexes, P. Andres, U. Schubert, Adv. Mater., 2004, 16, 1043.
  • A Heterometallo-​Supramolecular Polymer with Cu(I) and Fe(II) Ions Introduced Alternately, D. Hossain, J. Zhang, R. K. Pandey, T. Sato, M. Higuchi, , Eur. J. Inorg. Chem., 2014, 2014, 3763.
  • Photoinduced charge separation within metallo-supramolecular wires built around a [Ru(bpy)3]2+ bisterpyridine entity R. Farran, D. Jouvenot, B. Gennaro, F. Loiseau, J. Chauvin, A. Deronzier.. ACS Appl. Mater. Interfaces, 2016, 8, 16136.
Background and skills expected: We are looking for a student with knowledge on coordination chemistry, having large interest for chemical-physics characterization notably electrochemistry and stationary and time resolved emission spectroscopy

Competences that will be acquired during the internship: Practical in Electrochemistry (cyclic voltammetry) in glove box. Working with nanosecond and picosecond pulsed laser for emission measurements. Electrodeposition technics and surface imaging (AFM, SEM,…)