Synthesis, Spectroelectrochemical Behavior, and Chiroptical Switching of Tris(β-diketonato) Complexes of Ruthenium(III), Chromium(III), and Cobalt(III).

Five tris(β-diketonato) complexes of ruthenium(III), chromium(III), and cobalt(III) [Ru(Buacac) (1), Ru(Oacac) (2), Cr(Buacac) (3), Cr(Oacac) (4), and Co(Buacac) (5), where Buacac = 3-butylpentane-2,4-dionato and Oacac = 3-octylpentane-2,4-dionato] with a chiral propeller-like structure have been prepared. Ligands and complexes syntheses are presented together with characterization of the compounds by H and C NMR spectroscopy, mass spectrometry, IR, UV-vis, electronic circular dichroism (ECD) spectroscopy, electrochemistry studies, and first-principles calculations. The crystal structures of 1 and 5 have also been obtained and analyzed.

Elaboration of covalently linked polyoxometalates with ruthenium and pyrene chromophores and characteriation of their photophysical properties.

Keggin and Dawson-type polyoxometalates (POMs) decorated by organometallic [cyclometalated ruthenium(II) polypyridine complex] or organic (pyrene) chromophores were prepared by postfunctionalization of hybrid disilylated POM platforms. The connection is made in a very efficient and modular way via Sonogashira coupling reactions, which provide a rigid linkage between the POM and the photoactive centers. Electronic properties have been inferred from electrochemical and photophysical studies and reflect poor electronic interactions between both partners.