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Three Bis‐BODIPY Analogous Diruthenium Redox Series: Characterization and Electronic Structure Analysis
Author(s) -
Bera Sudip Kumar,
Mondal Sudipta,
Hazari Arijit Singha,
Priego José Luis,
JiménezAparicio Reyes,
Kaim Wolfgang,
Lahiri Goutam Kumar
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202000326
Subject(s) - ruthenium , chemistry , diimine , redox , cyclic voltammetry , differential pulse voltammetry , ligand (biochemistry) , bodipy , bipyridine , crystallography , electron paramagnetic resonance , stereochemistry , electrochemistry , photochemistry , medicinal chemistry , fluorescence , crystal structure , inorganic chemistry , catalysis , nuclear magnetic resonance , organic chemistry , biochemistry , physics , receptor , electrode , quantum mechanics
Abstract The dianion derived from (2 Z ,6 Z )‐3,7‐diphenyl‐N2,N6‐di(pyridin‐2‐yl)pyrrolo[2,3‐ f ]indole‐2,6(1H,5H)‐diimine (H 2 BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL 2 , L=2,4‐pentanedionato (acac − ), 2,2’‐bipyridine (bpy) or 2‐phenylazopyridine (pap) in [Ru(acac) 2 Ru(μ‐BL)Ru(acac) 2 ] ( 1 / 2 ), [Ru(bpy) 2 Ru(μ‐BL)Ru(bpy) 2 ](ClO 4 ) 2 ([ 3 ](ClO 4 ) 2 ) and [Ru(pap) 2 Ru(μ‐BL)Ru(pap) 2 ](ClO 4 ) 2 ([ 4 ](ClO 4 ) 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+ ).