title: Synthesis of heteroleptic anthryl-substituted beta-ketoenolates of rhodium(III) and iridium(III): photophysical, electrochemical, and EPR study of the fluorophore-metal interaction.
abstract: The anthryl-substituted rhodium(III) and iridium(III) heteroleptic beta-ketoenolato derivatives of general formula [M(acac)(2)(anCOacac)] [acac = pentane-2,4-dionate; anCOacac = 3-(9-anthroyl)pentane-2,4-dionate], 3 (M = Rh) and 4 (M = Ir), and [M(acac)(2)(anCH(2)acac)] [anCH(2)acac = 3-(9-anthrylmethyl)pentane-2,4-dionate], 5 (M = Rh) and 6 (M = Ir), were prepared by reacting the corresponding tris(pentane-2,4-dionate)metal complexes, [M(acac)(3)], with 9-anthroyl chloride and 9-chloromethylanthracene, respectively, under Friedel-Crafts conditions. 3-6 were characterized by elemental analysis, ion spray mass spectrometry (IS-MS), (1)H NMR, and UV-vis spectroscopy. The structure of 3 was also elucidated by single-crystal X-ray analysis. When excited at 365 nm, 3-6 result to be poorly luminescent compounds; while the free diketone, i.e., 3-(9-anthrylmethyl)pentane-2,4-dione 1, whose structure was established also by single-crystal X-ray analysis, results to be a strongly light emitting molecule. The study of the electrochemical behavior of 3-6 as well as of the corresponding tris-acetylacetonates of rhodium(III) and iridium(III) allows a satisfactory interpretation of their electrode process mechanism, and gives information about the location of the redox sites along with the thermodynamic and kinetic characterization of the corresponding redox processes. All data are in agreement with the hypothesis that the quenching of the anthracene fluorescence, observed for compounds 3-6, can be due to an intramolecular electron transfer process between the anthryl moiety and the metal-beta-ketoenolato component. Moreover, a study was carried out of the redox behavior of the dyads 3-6 under chemical activation. The one-electron oxidation of compounds 3-6 by thallium(III) trifluoroacetate leads to the formation of the corresponding cation radicals, 3(+)-6(+), whose highly resolved X-band EPR spectra were fully interpreted by computer simulation as well as by semiempirical and DFT calculations of spin density distribution.
authors.affiliation: Dipartimento di Chimica G. Ciamician, Università di Bologna, Via Selmi 2, 40126 Bologna, Italy.
authors.forename: Maurizio
authors.initials: M
authors.lastname: Carano
authors.forename: Francesca
authors.initials: F
authors.lastname: Cicogna
authors.forename: Julien L
authors.initials: JL
authors.lastname: Houben
authors.forename: Giovanni
authors.initials: G
authors.lastname: Ingrosso
authors.forename: Fabio
authors.initials: F
authors.lastname: Marchetti
authors.forename: Loïc
authors.initials: L
authors.lastname: Mottier
authors.forename: Francesco
authors.initials: F
authors.lastname: Paolucci
authors.forename: Calogero
authors.initials: C
authors.lastname: Pinzino
authors.forename: Sergio
authors.initials: S
authors.lastname: Roffia