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• W2046914733 endingPage "9347" @default.
• W2046914733 startingPage "9336" @default.
• W2046914733 abstract "Reaction between ferrocene lithium or ethynylferrocene magnesium bromide and (chloro)boronsubphthalocyanine leads to formation of ferrocene- (2) and ethynylferrocene- (3) containing subphthalocyanine dyads with a direct organometallic B–C bond. New donor–acceptor dyads were characterized using UV–vis and magnetic circular dichroism (MCD) spectroscopies, NMR method, and X-ray crystallography. Redox potentials of the rigid donor–acceptor dyads 2 and 3 were studied using the cyclic voltammetry (CV) and differential pulse voltammetry (DPV) approaches and compared to the parent subphthalocyanine 1 and conformationally flexible subphthalocyanine ferrocenenylmethoxide (4) and ferrocenyl carboxylate (5) dyads reported earlier. It was found that the first oxidation process in dyads 2 and 3 is ferrocene-centered, while the first reduction as well as the second oxidation are centered at the subphthalocyanine ligand. Density functional theory-polarized continuum model (DFT-PCM) and time-dependent (TD) DFT-PCM methods were used to probe the electronic structures and explain the UV–vis and MCD spectra of complexes 1–5. DFT-PCM calculations suggest that the LUMO, LUMO+1, and HOMO-3 in new dyads 2 and 3 are centered at the subphthalocyanine ligand, while the HOMO to HOMO-2 in both dyads are predominantly ferrocene-centered. TDDFT-PCM calculations on compounds 1–5 are indicative of the π → π* transitions dominance in their UV–vis spectra, which is consistent with the experimental data. The excited state dynamics of the parent subphthalocyanine 1 and dyads 2–5 were investigated using time-resolved transient spectroscopy. In the dyads 2–5, the initially excited state is rapidly (<2 ps) quenched by electron transfer from the ferrocene ligand. The lifetime of the charge transfer state demonstrates a systematic dependence on the structure of the bridge between the subphthalocyanine and ferrocene." @default.
• W2046914733 created "2016-06-24" @default.
• W2046914733 creator A5027041102 @default.
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• W2046914733 creator A5076918950 @default.
• W2046914733 creator A5079366084 @default.
• W2046914733 date "2014-08-14" @default.
• W2046914733 modified "2023-10-18" @default.
• W2046914733 title "Redox and Photoinduced Electron-Transfer Properties in Short Distance Organoboryl Ferrocene-Subphthalocyanine Dyads" @default.
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