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Isomeric Diruthenium Complexes Bridged by Deprotonated Indigo in cis and trans Configuration
Author(s) -
Chatterjee Madhumita,
Ghosh Prabir,
Beyer Katharina,
Paretzki Alexa,
Fiedler Jan,
Kaim Wolfgang,
Lahiri Goutam Kumar
Publication year - 2018
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.201701562
Subject(s) - deprotonation , indigo , chemistry , ring (chemistry) , electron paramagnetic resonance , crystallography , density functional theory , cis–trans isomerism , electrochemistry , ligand (biochemistry) , chelation , metal , crystal structure , stereochemistry , computational chemistry , inorganic chemistry , electrode , ion , organic chemistry , nuclear magnetic resonance , art , biochemistry , physics , receptor , visual arts
The doubly deprotonated form L 2− of indigo=H 2 L can bind two [Ru(acac) 2 ] complex fragments in the cis ( 1 ) and trans configuration ( 2 ), as evidenced from crystal structure analysis. While the latter type of N,O; N ’ ,O ’ coordination has been observed earlier, for example, with [Ru(bpy) 2 ] 2+ , leading to two equivalent six‐membered ring chelates, the cis arrangement in 1 is observed here for the first time in a dinuclear complex, producing one five‐membered ring chelate with N,N ’ coordination and one seven‐membered chelate with O,O ’ coordination. The different structures of the isomers result in differing electrochemical and spectroelectrochemical (EPR, UV‐Vis‐NIR) responses for various accessible charge states 1 n and 2 n , n =–, 0, +, 2+. The associated electronic structures were analyzed by DFT (structures, spin density) and TD‐DFT calculations (electronic transitions), revealing mainly metal‐based reduction but largely indigo ligand‐based oxidation of both neutral precursors.