ESR7 Project

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)
Secondment host: Elkem Silicones France (FR)
Academic secondment : UAB (Barcelona, ES)

Objectives

To synthesize light-responsive phosphine ligands containing photoisomerizable dithienylethene, azobenzene or stilbene groups [3], 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 [4], 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.

 

[1] R. Göstl, A. Senf, S. Hecht, Chem. Soc. Rev. 2014, 43, 1982-1996.
[2] V. Blanco, D. A. Leigh, V. Marcos, Chem. Soc. Rev.2015, 44, 5341-5370.
[3] 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.
[4] 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.

Anastasiia Sherstiuk

Anastasiia Sherstiuk

PhD student - ESR7

I come from Saint Petersburg, Russia. I have completed my Bachelor’s degree with honors at Saint-Petersburg State Technological Institute with a specialization in the chemical technology of the organic dyes and phototropic compounds. Afterwards, I switched to inorganic chemistry and got a Master’s degree with honors in Chemistry at ITMO University. My research was focused on the modification of hafnium oxide nanoparticles for drug delivery. During my Master’s studies I have completed an internship at Leipzig University in the group of Prof. Eva Hey-Hawkins where I was synthesizing polymers. Also I attended courses on « Synthetic Photochemistry and Photocatalysis »and « Electroorganic Synthesis » during 29th summer school at Jyväskylä. My PhD project is focused on the design of photoswitchable catalysts. The change of catalysts’ steric and electronic properties induced by the interaction with light leads to the difference in its catalytic activity (ON/OFF state) and enables to control in-situ the catalytic reaction.