Helicenes possess a unique screw-shape and p-conjugated structure which provides them with peculiar properties such as huge optical rotation values [1]. These helicene derivatives may have applications as chiroptical materials or in catalysis. We have investigated diverse routes for the molecular engineering of helicenes involving organometallic and coordination chemistry of helicene derivatives. Phosphole-modified azahelicenes that act as 1,4-P,N-chelates towards metal ions afforded chiral metal-bis(helicene) complexes (A  ) via stereoselective coordination [2]. The metal center has a great impact on the chiroptical properties of these novel helicene derivatives. Furthermore, the first organometallic helicenes (B  ) incorporating a transition metal into their ortho-annulated p-conjugated backbones [3a] have been prepared, by a simple ortho-metalation reaction and assemblies of platinahelicenes bearing an original Pt(III)-Pt(III) scaffold have revealed unprecedented enhancement of the chiroptical properties through sigma-pi conjugation [3b,c]. Finally, molecular redox chiroptical switches have been obtained by grafting ruthenium centers onto vinyl-helicene cores (C  , unpublished).[1] (a) Katz, T. J. Angew. Chem. Int. Ed. 2000  , 39, 1921. (b) Urbano, A. Angew. Chem. Int. Ed. 2003  , 42, 3986. (c) Martin, R. H. Angew. Chem. Int. Ed. 1974  , 13, 649.[2] (a) Graule, S.; Rudolph, M.; Vanthuyne, N.; Autschbach, J.; Roussel, C.; Crassous, J.; R�au, R. J. Am. Chem. Soc., 2009, 131, 3183. (b) Graule, S.; Rudolph, M.; Shen, W.; Williams, J. A. G.; Lescop, C.; Autschbach, J.; Crassous, J.; R�au, R. Chem. Eur. J., 2010, 16, 5976.[3] (a) Norel, L.; Rudolph, M.; Vanthuyne, N.; Williams, J. A. G.; Lescop, C.; Roussel, C.; Autschbach, J.; Crassous, J.; R�au, R. Angew. Chem. Int. Ed., 2010  , 49, 99. (b) Anger, E.; Rudolph, M.; Shen, C.; Vanthuyne, N.; Toupet, L.; Roussel, C.; Autschbach, J.; Crassous, J.; R�au, R. J. Am. Chem. Soc., 2011  , 133, 3800. (c) Anger, E.; Rudolph, M.; Norel, L.; Zrig, S.; Shen, C.; Vanthuyne, N.; Toupet, L.; Williams, J. A. G.; Roussel, C.; Autschbach, J.; Crassous, J.; R�au, R. Chem. Eur. J., 2011  , 17, 14178.

Coordination and organometallic chemistry of helicene derivatives

244th National Meeting (2012)

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