Three Bis‐BODIPY Analogous Diruthenium Redox Series: Characterization and Electronic Structure Analysis |
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| Authors: | Sudip Kumar Bera,Sudipta Mondal,Arijit Singha Hazari,Jos Luis Priego,Reyes Jim nez‐Aparicio,Wolfgang Kaim,Goutam Kumar Lahiri |
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| Affiliation: | Sudip Kumar Bera,Sudipta Mondal,Arijit Singha Hazari,José Luis Priego,Reyes Jiménez‐Aparicio,Wolfgang Kaim,Goutam Kumar Lahiri |
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| Abstract: | The dianion derived from (2Z,6Z)‐3,7‐diphenyl‐N2,N6‐di(pyridin‐2‐yl)pyrrolo[2,3‐f]indole‐2,6(1H,5H)‐diimine (H2BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL2, L=2,4‐pentanedionato (acac?), 2,2’‐bipyridine (bpy) or 2‐phenylazopyridine (pap) in [Ru(acac)2Ru(μ‐BL)Ru(acac)2] ( 1 / 2 ), [Ru(bpy)2Ru(μ‐BL)Ru(bpy)2](ClO4)2 ([ 3 ](ClO4)2) and [Ru(pap)2Ru(μ‐BL)Ru(pap)2](ClO4)2 ([ 4 ](ClO4)2). The compounds, including a diastereoisomeric pair 1 (meso) and 2 (rac) were spectroscopically and structurally characterized. Reversible electron transfers as revealed by cyclic and differential pulse voltammetry allowed for an EPR and UV‐vis‐NIR spectroelectrochemical investigation of several neighboring charge states. Together with susceptibility measurements and TD‐DFT calculations the assignment of oxidation states reveals that 1 , 2 are diruthenium(III) species which can be oxidized or reduced by one electron whereas 3 2+ and 4 2+ contain ruthenium(II) and get reduced or oxidized mainly at the dianionic bridge ( 3 2+) or are reduced at the ancillary ligands pap ( 4 2+). |
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| Keywords: | Ruthenium aza-BODIPY structure spectroelectrochemistry redox non-innocence |
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