Thèse de Gaëtan Basuyaux

Chiral metal-functionalized hydrogen-bonded polymers

Projet de recherche en cours.

Laboratoires co-porteurs
Mots clés

Metal-functionalized polymers • Sergeants-and-soldiers principle • Platinum complexes • Chirality transfer References.

Projet de recherche
  1. In this collaborative research project we describe the preparation of novel class of metal-functionalized hydrogen-bonded polymers. The latter presents several attractive features:  the assemblies will be stimuli-responsive since mainly based on highly directional and dynamic hydrogen bonds,
  2. the structure and properties of the assemblies will be tuned as a function of the interactions between the lateral metal complexes, and
  3. intrinsically achiral metal complexes will be located within the chiral environment displayed by the hydrogen-bonded assemblies. Thus controlling these non-covalent interactions allows chiral information amplification into dynamic helical polymers of metallo-luminophores.(1)

The drawing below shows the different classes of metal-functionalized monomers that are currently under investigation (Figure 1).

Figure 1. Different classes of metal-functionalized monomers under investigation.
Figure 1. Different classes of metal-functionalized monomers under investigation.

In particular, platinum(II) bis-urea monomers were prepared and characterized (Figure 2). The solution behavior of these hybrid monomers was examined by mixing them with optically active bis urea monomers which behave as sergeants. This effect allows the chiral transfer and amplification towards the environment of the metal complex using small portion of optically active molecules at the supramolecular level.(2)

Figure 2. Optically active bis-urea (sergeant) and hybrid metallo-functionalized monomers (soldier).
Figure 2. Optically active bis-urea (sergeant) and hybrid metallo-functionalized
monomers (soldier).

On the other hand, several novel enantiopure benzene-1,3-5-tricarboxamide (BTAs) were prepared which are functionalized by nitrogen donors atoms in their side chains.(3) Functionalization of these molecules by various metal complexes is currently underway.

Références
  • (1)-Dubarle-Offner, J. Moussa, H. Amouri, B. Jouvelet, L. Bouteiller, M. Raynal, Chem. Eur. J. 2016, 22, 3985-3990.
  • (2)-R. A. Palmans, E. W. Meijer, Angew. Chem. Int. Ed., 2007, 46, 8948-8978.
  • (3)-S. Cantekin, T. F. A. de Greef, A. R. A. Palmans, Chem. Soc. Rev., 2012, 41, 6125-6132. M. Raynal, F. Portier, P. W. N. M. van Leewen, L. Bouteiller, J. Am. Chem. Soc. 2013, 16, 17687-17690.