Polymorphism in a π-Stacked 1,3,2-Dithiazolyl Radical: Pyridyl-1,3,2-Dithiazolyl
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http://dx.doi.org/10.1021/cg7010056 |
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Title
Polymorphism in a π-Stacked 1,3,2-Dithiazolyl Radical: Pyridyl-1,3,2-DithiazolylAuthor (s)
Date
2008-01Publisher
American Chemical SocietyISSN
1528-7483Bibliographic citation
Crystal Growth and Design, 8, 1, p. 155-161Type
info:eu-repo/semantics/articlePublisher version
http://pubs.acs.org/doi/abs/10.1021/cg7010056Version
info:eu-repo/semantics/publishedVersionAbstract
Pyridyl-1,3,2-dithiazolyl PyDTA (1) has been synthesized and its electronic structure has been probed by cyclic
voltammetry, electron paramagnetic resonance spectroscopy, and density functional theory calculations. ... [+]
Pyridyl-1,3,2-dithiazolyl PyDTA (1) has been synthesized and its electronic structure has been probed by cyclic
voltammetry, electron paramagnetic resonance spectroscopy, and density functional theory calculations. The results demonstrate
that the spin distribution and redox properties of the radical are intermediate between those observed for the isoelectronic benzoand pyrazino-1,3,2-dithiazolyl radicals. Crystals of 1 can be grown by vacuum sublimation as two polymorphs. The kinetically
favored form 1r grows as purple/black blocks or rods and crystallizes in the noncentric space group P21, while the thermodynamically
favored 1 phase forms green/black shards and crystallizes in the centric space group P21/n. The structures of both 1r and 1
comprise layers of head-to-head π*-π* dimers in the ab plane. The two structures differ in the orientation of the π-dimers along
the stacks. In 1r dimers are aligned head-to-head, while in 1 the orientation of the dimers alternates in a head-over-tail fashion,
so as to produce an approximate doubling of the crystallographic c-axis in relation to 1r. Variable temperature magnetic susceptibility
measurements reveal that both phases are essentially diamagnetic at low temperatures. Above 180 K (for 1 ) and above 250 K (for
1r) the free Curie spin count for both polymorphs begins to rise, indicating a weakening of the π*-π* dimers in the solid state. [-]
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