Photo-switchable phosphines for in situ modification of catalysts
Recruting institution: ULEI.
Diploma-delivering institutions: ULEI, UAB.
Thesis co-directors: Evamarie Hey-Hawkins ( ULEI , Leipzig, DE), Rosa Maria Sebastián (UAB, Barcelona, ES)
Seondment host: Elkem Silicones France (FR)
Objectives: To synthesize light-responsive phosphine ligands containing photoisomerizable dithienylethene, azobenzene or stilbene groups , remotely placed from the catalytic center. The photoinduced severe geometric and/or electronic changes will affect the coordinating ability and/or electronic communication with metals , thus resulting in light-controlled modification of the catalytic activity [1,2]. The effect will be rationalized using theoretical calculations (collaboration with Agustí Lledós, UAB), which will facilitate further rational design of improved light-responsive catalysts. R. Göstl, A. Senf, S. Hecht, Chem. Soc. Rev. 2014, 43, 1982-1996.  V. Blanco, D. A. Leigh, V. Marcos, Chem. Soc. Rev.2015, 44, 5341-5370.  M. Izquierdo-Serra, M. Gascón-Moya, J. J. Hirtz, S. Pittolo, K. E. Poskanzer, E. Ferrer, R. Alibés, F. Busqué, R. Yuste, J. Hernando, P. Gorostiza, J. Am. Chem. Soc. 2014, 136, 8693-8701.  P. Neumann, H. Dib, A.-M. Caminade, E. Hey-Hawkins, ACIE 2015, 54, 311-314.
Expected Results: Development of optimized new families of phosphine ligands with different coordinating behavior and/or electronic communication upon photoisomerization. Activity ratio of at least 100 between the two photostates in at least 3 catalytic applications. Full reversibility of the photoswitching for at least 5 cycles. Scaling up and industrial valorization.