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Non‐classical S‐Heteroacenes with o ‐Quinoidal Conjugation and Open‐Shell Diradical Character
Author(s) -
Shi Xueliang,
Gopalakrishna Tullimilli Y.,
Wang Qing,
Chi Chunyan
Publication year - 2017
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.201701813
Subject(s) - diradical , chemistry , dimer , character (mathematics) , open shell , reactivity (psychology) , derivative (finance) , stereochemistry , crystallography , alternation (linguistics) , organic chemistry , physics , quantum mechanics , medicine , linguistics , geometry , mathematics , alternative medicine , philosophy , pathology , singlet state , financial economics , economics , excited state
A series of non‐classical S‐heteroacenes were synthesized and exhibited intriguing physical properties and chemical reactivities that are very different from classical acenes. X‐ray crystallographic analyses revealed that all acenothiophene derivatives Ph‐AT‐1 – Ph‐AT‐3 had an o ‐quinoidal π‐conjugation with large bond‐length alternation, whereas the acenodithiophene derivative Ph‐ADT‐3 easily dimerized or reacted with oxygen to form a peroxy‐bridged dimer. The long acenothiophene Ph‐AT‐4 was also highly reactive. The origin of these unique properties was investigated carefully by both experiments and theoretical calculations. The high reactivity of the long non‐classical S‐heteroacenes can be explained by their intrinsic open‐shell diradical character as well as the o ‐quinoidal conjugation.