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Trimethyltetrathiafulvalene Bearing an N ‐Methylpyridinium Substituent: Synthesis, Crystal Structures, and Charge Transfer Properties
Author(s) -
Moore Adrian J.,
Batsanov Andrei S.,
Bryce Martin R.,
Howard Judith A. K.,
Khodorkovsky Vladimir,
Shapiro Lev,
Shames Alex
Publication year - 2001
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(200101)2001:1<73::aid-ejoc73>3.0.co;2-0
Subject(s) - chemistry , substituent , charge (physics) , bearing (navigation) , crystal structure , stereochemistry , crystallography , physics , quantum mechanics , cartography , geography
The synthesis of 4,4′,5‐trimethyl‐5′‐(4‐pyridyl)tetrathiafulvalene ( 3 ), has been accomplished by reaction of the stannylated precursor 2 with 4‐bromopyridine. Alkylation of 3 affords the N ‐methylpyridinium salt 4 which displays intramolecular charge transfer properties in solution as deduced from UV/Vis spectra, cyclic voltammetric data, and semiempirical quantum mechanical calculations. The X‐ray crystal structures of neutral molecule 3 , the salt ( 4 + )I − and the charge transfer salt ( 4 + ) 2 (TCNQ 3 ) 2− · are reported. The positive charge in ( 4 + )I − and ( 4 + ) 2 (TCNQ 3 ) 2− · is predominantly confined on the pyridinium ring. The structure of ( 4 + ) 2 (TCNQ 3 ) 2− · comprises segregated stacks of cations and TCNQ radical anions, with the anions overlapping in the usual ring‐over‐bond fashion. This salt is a semiconductor (σ rt = 10 −2 S cm −1 ).