π‑Extended
Thiadiazoles Fused with Thienopyrrole
or Indole Moieties: Synthesis, Structures, and Properties
Shin-ichiro Kato
Takayuki Furuya
Atsushi Kobayashi
Masashi Nitani
Yutaka Ie
Yoshio Aso
Toshitada Yoshihara
Seiji Tobita
Yosuke Nakamura
10.1021/jo301458m.s004
https://acs.figshare.com/articles/dataset/_Extended_Thiadiazoles_Fused_with_Thienopyrrole_or_Indole_Moieties_Synthesis_Structures_and_Properties/2489437
We report the syntheses, structures, photophysical properties,
and redox characteristics of donor–acceptor-fused π-systems,
namely π-extended thiadiazoles <b>1</b>–<b>5</b> fused with thienopyrrole or indole moieties. They were synthesized
by the Stille coupling reactions followed by the PPh<sub>3</sub>-mediated
reductive cyclizations as key steps. X-Ray crystallographic studies
showed that isomeric <b>1b</b> and <b>2b</b> form significantly
different packing from each other, and <b>1a</b> and <b>4a</b> afford supramolecular networks via multiple hydrogen bonding with
water molecules. Thienopyrrole-fused compounds <b>1b</b> and <b>2b</b> displayed bathochromically shifted intramolecular charge-transfer
(CT) bands and low oxidation potentials as compared to indole-fused
analog <b>3b</b> and showed moderate to good fluorescence quantum
yields (Φ<sub>f</sub>) up to 0.73. In <b>3b</b>–<b>5b</b>, the introduction of electron-donating substituents in
the indole moieties substantially shifts the intramolecular CT absorption
maxima bathochromically and leads to the elevation of the HOMO levels.
The Φ<sub>f</sub> values of <b>3</b>–<b>5</b> (0.04–0.50) were found to be significantly dependent on the
substituents in the indole moieties. The OFET properties with <b>1b</b> and <b>2b</b> as an active layer were also disclosed.
2016-02-20 12:28:13
indole moieties
intramolecular CT absorption maxima bathochromically
2 b
isomeric 1 b
substituent
HOMO
2 b form
Φ f values
OFET