Excited state properties and energy transfer within dipyrrin-based binuclear iridium/platinum dyads : The effect of ortho-methylation on the spacer
Articolo
Data di Pubblicazione:
2012
Citazione:
Excited state properties and energy transfer within dipyrrin-based binuclear iridium/platinum dyads : The effect of ortho-methylation on the spacer / C. Bronner, M. Veiga, A. Guenet, L. De Cola, M.W. Hosseini, C.A. Strassert, S.A. Baudron. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 18:13(2012), pp. 4041-4050. [10.1002/chem.201103836]
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) 2Ir(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. Luminescent, cyclometalated iridium complexes based on pyridyl-appended dipyrrin ligands were prepared and characterized both in the solid state and in solution. The consequence of the functionalization of the peripheral pyridyl moiety or its coordination to metal centers on the emission properties of mononuclear or heterobinuclear complexes was studied by systematic photophysical investigations.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
cyclometalated complexes; dipyrrin ligands; iridium; luminescence; platinum
Elenco autori:
C. Bronner, M. Veiga, A. Guenet, L. De Cola, M.W. Hosseini, C.A. Strassert, S.A. Baudron
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