PhD offer (ROCS group) – Synthesis of pi-Functional Molecules through 1,3-Dipolar Cycloaddition of Polycyclic Aromatic Azomethine Ylides and Silicon or Germanium Dipolarophiles

The ROCS group, in partnership with Prof. Shingto ITO’s group at Nanyang Technological University (NTU) in Singapore, is looking for a candidate for a PhD scholarship on the topic:

Synthesis of π-Functional Molecules through 1,3-Dipolar Cycloaddition of Polycyclic Aromatic Azomethine Ylides and Silicon or Germanium Dipolarophiles

Project overview :  

Link of the offer

Incorporation of group 14 heteroatoms Si and Ge in p-conjugated molecules confers interesting electronic characteristics to the parent structure.1 Inclusion of Si is increasingly frequent and this strategy has opened new perspectives for the design of functional materials. Conversely, less work has been focused on Ge congeners. It is important to underscore that the accessibility to such Si- and Ge-containing molecules relies heavily on the development of appropriate synthetic methodology for C–Si and C–Ge bond formation.

The Ito group has developed the use of polycyclic aromatic azomethine ylides (e.g. 1) as versatile building blocks to prepare polycyclic aromatic hydrocarbons (PAHs) containing a fused pyrrole unit (e.g. 2) through 1,3-dipolar cycloaddition / oxidation sequences. This strategy has been implemented with an array of (cyclic) alkenes to prepare original PAHs with diverse functionalities of interest for material chemistry.2 Introduction of Si or Ge atoms to the fused pyrrole PAH frameworks should add novel functionalities such as emissive properties.3 To evaluate this prospect, the objective of our proposal is to develop Si- or Ge-containing dipolarophiles competent to be engaged with in the 1,3-dipolar cycloaddition / oxidation sequence, and thereby access unprecedented Si- or Ge-containing PAHs. The originality of the work will be related to the development of innovative synthetic methodology and to the characterisation of new functional molecules.

Consortium and International Cooperation

The proposal stems from the combination of the complementary expertise’s of the two research groups. On the one hand, the ROCS group from Sorbonne Université has a recognised know-how in the field of synthetic methodology of organosilanes and organogermanes which will be essential to design and prepare the requisite Si and Ge dipolarophiles.4 On the other hand, the group of Prof. Ito has a longstanding interest in designing, preparing and characterizing unprecedented PAHs with fused pyrrole structures.2 This collaboration will offer a unique opportunity to evaluate the influence of incorporation of Si and Ge atoms to the pyrrole-based PAH core, with the outermost aim of finding molecules with original functionalities.

The project is associated to the Chemistry, Materials and Interfaces initiative. The experimental work will be carried out in both laboratories as the doctoral project (dual SU and NTU degree) includes a research stay in Singapore of 12 months.

Profiles : 

Training in organic and organometallic chemistry with an interest in methodology and physical organic chemistry.

Duration:

36 months (stay in Singapore of 12 months) from October 2024

Application:

– a detailed CV
– the grades for Master 2 degree
Deadline 15/05/2024

References:

  1. a) K. Tamao, M. Uchida, T. Izumizawa, F. Furukawa, S. Yamaguchi, J. Am. Chem. Soc. 1996118, 11974.
    b) T. A. Su, H. Li, R. S. Klausen, N. T. Kim, M. Neupane, J. L. Leighton, M. L. Steigerwald, L. Venkataraman, C. Nuckolls, Acc. Chem. Res. 201750, 1088.
    c) J. Ohshita, M. Sugino, Y. Ooyama, Y. Adachi, Organometallics 201938, 1606.
  2. Selected references: a) S. Ito, Y. Tokimaru, K. Nozaki, Chem. Commun. 201551, 221.
    b) S. Ito, Y. Tokimaru, K. Nozaki, Angew. Chem. Int. Ed. 201554, 7256.
    c) Y. Tokimaru, S. Ito, K. Nozaki, Angew. Chem. Int. Ed. 201756, 15560.
    d) X. Zhang, M. R. Mackinnon, G. J. Bodwell, S. Ito, Angew. Chem. Int. Ed. 202261, e202116585.
    e) W. Wang, F. Hanindita, Y. Tanaka, K. Ochiai, H. Sato, Y. Li, T. Yasuda, S. Ito, Angew. Chem. Int. Ed. 202362, e202218176.
    f) Y. Hamamoto, K. Ochiai, Y. Li, E. Tapavicza, S. Ito, Angew. Chem. Int. Ed. 202463, e202319022.
  3. Y. Yabusaki, N. Ohshima, H. Kondo, T. Kusamoto, Y. Yamanoi, H. Nishihara, Chem. Eur. J. 201016, 5581.
  4. Selected references: a) E. Romain, C. Fopp, F. Chemla, F. Ferreira, O. Jackowski, M. Oestreich, A. Perez-Luna, Angew. Chem. Int. Ed. 201453, 11333.
    b) E. Romain, K. de la Vega-Hernández, F. Guégan, J. S. García, C. Fopp, F. Chemla, F. Ferreira, H. Gerard, O. Jackowski, S. Halbert, M. Oestreich, A. Perez-Luna, Adv. Synth. Catal. 2021363, 2634.
    c) K. de la Vega-Hernández, E. Romain, A. Coffinet, K. Bijouard, G. Gontard, F. Chemla, F. Ferreira, O. Jackowski, A. Perez-Luna, J. Am. Chem. Soc. 2018140, 17632.
    d) S. Kassamba, A. Perez-Luna, F. Ferreira, M. Durandetti, Chem. Commun. 202258, 3901.