Switching of excited states in cyclometalated platinum complexes incorporating pyridyl-acetylide ligands (Pt-C[triple bond, length as m-dash]C-py): a combined experimental and theoretical study - Université de Rennes Accéder directement au contenu
Article Dans Une Revue New Journal of Chemistry Année : 2011

Switching of excited states in cyclometalated platinum complexes incorporating pyridyl-acetylide ligands (Pt-C[triple bond, length as m-dash]C-py): a combined experimental and theoretical study

Résumé

This article presents the design of cyclometalated platinum(II) complexes incorporating pyridyl-appended acetylide ligands of the form Pt-C[triple bond, length as m-dash]C-py, acting either as sites for protonation or methylation reactions or as a host receptor for binding metal cations. The complexes studied are Pt(t-Bu2phbpy)(-C[triple bond, length as m-dash]C-py), 2, which can undergo protonation at the pyridyl N; its cationic N-methylated derivative [Pt(t-Bu2phbpy)(-C[triple bond, length as m-dash]C-pyMe)]+, 4, which serves as a model of the N-protonated species; and a derivative in which the pyridyl ring is incorporated into a macrocyclic diamide-crown ether ligand (3). The co-ligand t-Bu2phbpy is a cyclometalated, N[caret]N[caret]C-coordinated phenylbipyridine ligand carrying tert-butyl groups at the 4-positions of the pyridyl rings. The photophysical properties of the neutral compounds 2 and 3 have been compared to those of the pyridinium, methyl-pyridinium or metal-complexed species (namely 2-H+, 4 and 3-Pb2+). Detailed TD-DFT calculations provide a theoretical basis to account for the experimentally-observed changes upon protonation/methylation/complexation. The joint TD-DFT and experimental studies provide evidence for an unprecedented molecular switch in the nature of the excited state (from mixed L′LCT/MLCT to ML′CT) in which the acceptor ligand in the CT process switches from being the N[caret]N[caret]C ligand to the pyridyl acetylide.
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Dates et versions

hal-00860209 , version 1 (10-09-2013)

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Camille Latouche, Pierre-Henri Lanoe, J. A. Gareth Williams, Véronique Guerchais, Abdou Boucekkine, et al.. Switching of excited states in cyclometalated platinum complexes incorporating pyridyl-acetylide ligands (Pt-C[triple bond, length as m-dash]C-py): a combined experimental and theoretical study. New Journal of Chemistry, 2011, 35 (10), pp.2196-2202. ⟨10.1039/C1NJ20225A⟩. ⟨hal-00860209⟩
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