Yu, Lianhe Muthukumaran, Kannan Sazanovich, Igor V. Kirmaier, Christine Hindin, Eve Diers, James R. Boyle, Paul D. Bocian, David F. Holten, Dewey Lindsey, Jonathan S. Excited-State Energy-Transfer Dynamics in Self-Assembled Triads Composed of Two Porphyrins and an Intervening Bis(dipyrrinato)metal Complex The synthesis and characterization of various triads composed of a linear array of two zinc porphyrins joined via an intervening bis(dipyrrinato)metal(II) complex are reported. The preparation exploits the facile complexation of dipyrrins with divalent metal ions to give bis(dipyrrinato)metal(II) complexes [abbreviated (dp)<sub>2</sub>M]. Copper(II) and palladium(II) chelates of dipyrrins (available by oxidation of dipyrromethanes) were prepared in 50−80% yield. A one-flask synthesis of bis(dipyrrinato)zinc(II) complexes was developed by oxidation of a dipyrromethane with DDQ or <i>p</i>-chloranil in the presence of Zn(OAc)<sub>2</sub>·2H<sub>2</sub>O in THF (∼80% yield). Three routes were developed for preparing porphyrin-dipyrrins:  (1) Suzuki coupling of a boronate-substituted zinc porphyrin (ZnP) and bis[5-(4-iodophenyl)dipyrrinato]Pd(II) to give the (ZnP-dp)<sub>2</sub>Pd triad (50% yield), followed by selective demetalation of the (dp)<sub>2</sub>Pd unit by treatment with 1,4-dithiothreitol under neutral conditions (71% yield); (2) oxidation of a porphyrin-dipyrromethane with <i>p</i>-chloranil in the presence of Zn(OAc)<sub>2</sub>·2H<sub>2</sub>O followed by chromatography on silica gel (71% yield); and (3) condensation of a dipyrrin-dipyrromethane and a dipyrromethane-dicarbinol under InCl<sub>3</sub> catalysis followed by oxidation with DDQ (10−16% yield). Four triads of form (ZnP-dp)<sub>2</sub>Zn were prepared in 83−97% yield by treatment of a porphyrin-dipyrrin with Zn(OAc)<sub>2</sub>·2H<sub>2</sub>O at room temperature. Free base dipyrrins typically absorb at 430−440 nm, while the bis(dipyrrinato)metal complexes absorb at 460−490 nm. The fluorescence spectra/yields and excited-state lifetimes of the (ZnP-dp)<sub>2</sub>Zn triad in toluene show (1) efficient energy transfer from the bis(dipyrrinato)zinc(II) chromophore to the zinc porphyrins (98.5% yield), and (2) little or no quenching of the resulting excited zinc porphyrin relative to the isolated chromophore. Taken together, these results indicate that bis(dipyrrinato)zinc(II) complexes can serve as self-assembling linkers that further function as secondary light-collection elements in porphyrin-based light-harvesting arrays. 2 Zn;zinc porphyrins;THF;zinc porphyrin;oxidation;DDQ;bi;InCl 3 catalysis;2 Pd unit;2 Zn triad;Free base dipyrrins;energy transfer;divalent metal ions;complex;room temperature;preparation exploits 2003-09-17
    https://acs.figshare.com/articles/journal_contribution/Excited-State_Energy-Transfer_Dynamics_in_Self-Assembled_Triads_Composed_of_Two_Porphyrins_and_an_Intervening_Bis_dipyrrinato_metal_Complex/3582294
10.1021/ic034559m.s002