title: Photoinduced electron transfer in platinum(II) terpyridinyl acetylide complexes connected to a porphyrin unit.
abstract: A series of six new dyads consisting of a zinc or magnesium porphyrin appended to a platinum terpyridine acetylide complex via a para-phenylene bisacetylene spacer are described. Different substituents on the 4' position of the terpyridinyl ligand were explored (OC7H15, PO3Et2, and H). The ground-state electronic properties of the dyads are studied by electronic absorption spectroscopy and electrochemistry, and they indicate some electronic interactions between the porphyrin subunit and the platinum complex. The photophysical properties of these dyads were investigated by steady-state, time-resolved, and femtosecond transient absorption spectroscopy in N,N-dimethylformamide solution. Excitation of the porphyrin unit leads to a very rapid electron transfer (2-20 ps) to the nearby platinum complex followed by an ultrafast charge recombination, thus preventing any observation of the charge separated state. The variation in the rate of the photoinduced electron transfer in the series of dyads is consistent with Marcus theory. The results underscore the potential of the para-phenylene bisacetylene bridge to mediate a rapid electron transfer over a long donor-acceptor distance.
authors.affiliation: Laboratoire de Synthèse Organique, UMR 6513 CNRS, FR CNRS 2465, Faculté des Sciences et des Techniques de Nantes, BP 92208, 2 rue de la Houssinière, 44322 Nantes Cedex 03, France.
authors.forename: Cyrille
authors.initials: C
authors.lastname: Monnereau
authors.forename: Julio
authors.initials: J
authors.lastname: Gomez
authors.forename: Errol
authors.initials: E
authors.lastname: Blart
authors.forename: Fabrice
authors.initials: F
authors.lastname: Odobel
authors.forename: Staffan
authors.initials: S
authors.lastname: Wallin
authors.forename: Anna
authors.initials: A
authors.lastname: Fallberg
authors.forename: Leif
authors.initials: L
authors.lastname: Hammarström