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Redox Switching in Ethenyl‐Bridged Bisphospholes
Author(s) -
Arkhypchuk Anna I.,
Mijangos Edgar,
Lomoth Reiner,
Ott Sascha
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405525
Subject(s) - hypsochromic shift , redox , deprotonation , chemistry , electrochemistry , absorption (acoustics) , photochemistry , topology (electrical circuits) , inorganic chemistry , organic chemistry , materials science , electrode , physics , ion , mathematics , quantum mechanics , combinatorics , composite material , fluorescence
A 2e − /2H + redox platform has been implemented in the ethenyl‐bridged bisphosphol‐3‐ol 1 to afford the first phospholes that feature chemically reversible oxidations. Oxidation of the title compounds to the corresponding bisphosphol‐3‐one 2 leads to a change in conjugation topology and a concomitant hypsochromic shift of the lowest‐energy absorption maximum by 100 nm. Electrochemical oxidation proceeds without any detectable intermediates, whereas the deprotonated form of 1 can be observed in an aprotic medium during the reduction of 2 . This dianionic intermediate 3 is characterized by end absorptions that are bathochromically shifted by circa 200 nm compared to those of 2 .