Premium
2,6‐Dialkoxy‐9,10‐bis(1,3‐dithiol‐2‐ylidene)‐9,10‐dihydroanthracene Derivatives: Synthesis, Electrochemistry and X‐ray Crystal Structures of Neutral and Dication Species
Author(s) -
Bryce Martin R.,
Finn Terry,
Batsanov Andrei S.,
Kataky Ritu,
Howard Judith A. K.,
Lyubchik Svetlana B.
Publication year - 2000
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 - 10.1002/1099-0690(200004)2000:7<1199::aid-ejoc1199>3.0.co;2-f
Subject(s) - dication , chemistry , dihedral angle , anthracene , crystallography , dimer , crystal structure , electrochemistry , ring (chemistry) , dithiol , molecule , radical ion , photochemistry , ion , hydrogen bond , electrode , organic chemistry
The synthesis of 2,6‐dialkoxy‐9,10‐bis(1,3‐dithiol‐2‐ylidene)‐9,10‐dihydroanthracene derivatives 15 and 16 is described. Solution electrochemistry shows that 15 and 16 display three redox waves, representing the sequential formation of the dication, radical trication and tetracation species in an E q E q E q process. The X‐ray crystal structures of neutral compounds 15 and 16 and the charge transfer complex ( 15 ) 2+ (TCNQ −• ) 2 · 2MeCN are reported. The neutral molecules adopt a saddle‐like conformation; the bis(1,3‐dithiole)benzoquinone system is U‐shaped through an ‘accumulating bend’ comprising the boat conformation of the central (quinonoid) ring and folding of both 1,3‐dithiole rings. In the complex ( 15 ) 2+ (TCNQ −• ) 2 · 2MeCN the anthracene system is planar and aromatic; the dithiolium cations form a dihedral angle of 78° with the anthracene plane. The TCNQ anion radicals form a stack of dimers with interplanar separations of 3.15 Å within a dimer and 3.50 Å between the dimers. The structure contains unusually short intermolecular S ··· N contacts [2.865(3) Å].