title: Excited state properties and energy transfer within dipyrrin-based binuclear iridium/platinum dyads: the effect of ortho-methylation on the spacer.
abstract: Luminescent cyclometalated iridium complexes based on pyridyl appended dipyrrin ligands were prepared and characterized both in the solid state and in solution. The functionalization of the peripheral pyridyl moiety causes dramatic changes on the emission properties of both mono- and hetero- binuclear complexes. A detailed photophysical investigation of the two mononuclear derivatives of the [(Ppy)(2)Ir(dpm-py)] family (Ppy=2-phenylpyridine, dpm-py=5-(4-pyridyl)dipyrrin) was carried out. Introduction of methyl groups at the 3 and 5 positions on the pyridyl unit diminishes the non-radiative rate constant by locking the peripheral pyridyl group orthogonally to the dipyrrinato plane. Thus, they limit the rotational degree of freedom, as well as the charge-transfer character of the excited state. The coordination of these two complexes to a cyclometalated [(dppy)Pt] fragment (dppy=2,6-diphenylpyridine) led to the formation of binuclear species in which the iridium and platinum complexes behave as acceptors and donors, respectively. In these heterobinuclear compounds, the methyl groups do not influence the energy transfer efficiency, which is estimated to be above 90 %. However, they do limit the charge-transfer character of the acceptor's excited state, as well as its rotational degree of freedom, thus avoiding the detrimental effect upon the photophysical performance.
authors.affiliation: Laboratoire de Chimie de Coordination Organique, UMR UdS-CNRS 7140, Institut Le Bel, Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg cedex, France.
authors.forename: Catherine
authors.initials: C
authors.lastname: Bronner
authors.forename: Manoel
authors.initials: M
authors.lastname: Veiga
authors.forename: Aurélie
authors.initials: A
authors.lastname: Guenet
authors.forename: Luisa
authors.initials: L
authors.lastname: De Cola
authors.forename: Mir Wais
authors.initials: MW
authors.lastname: Hosseini
authors.forename: Cristian A
authors.initials: CA
authors.lastname: Strassert
authors.forename: Stéphane A
authors.initials: SA
authors.lastname: Baudron