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2,5‐Disubstituted N, N′ ‐Dicyanoquinone Diimines (DCNQIs) − Syntheses and Redox Properties
Author(s) -
Hünig Siegfried,
Bau Robert,
Kemmer Martina,
Meixner Hubert,
Metzenthin Tobias,
Peters Karl,
Sinzger Klaus,
Gulbis Juris
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199802)1998:2<335::aid-ejoc335>3.0.co;2-a
Subject(s) - chemistry , substituent , quinone , cyclic voltammetry , redox , trifluoromethyl , fluoride , homo/lumo , medicinal chemistry , chloride , electron transfer , deuterium , crystallography , stereochemistry , photochemistry , organic chemistry , inorganic chemistry , electrochemistry , molecule , electrode , alkyl , physics , quantum mechanics
Abstract Quinones 1a − q and DCNQIs 2a − g have been synthesized in order to investigate substituent effects. It was necessary to employ novel synthetic routes for the introduction of iodine into 1f ( 7 ), the trifluoromethyl group into 1g − i , deuterium into 1m − p , and especially for the chloride/fluoride exchange of 1j to 1k , and 1l . With few exceptions both 1 and 2 undergo reversible electron transfer in two steps including thermodynamically very stable radical cations (lg K SEM > 10, cyclic voltammetry). Linear correlations have been found between E 2 (OX/SEM) data of 1 and 2 with (σ m + σ p )/2 and between E 2 of 1 and 2 . Correlations have also been found between E 2 and the LUMO energies of 1 and 2 . The crystal structure of quinone 1i shows some special interactions due to the two CF 3 groups, whereas the structures of DCNQIs 2d and 2g link up with those evaluated earlier.