Near-Infrared Electrochromic Behavior of Dibenzothiepin Derivatives Attached with Two Michler's Hydrol Blue Units.
Chemistry
; 28(70): e202202457, 2022 Dec 15.
Article
in En
| MEDLINE
| ID: mdl-36109342
ABSTRACT
10,11-Bis[bis(4-dimethylaminophenyl)methylene]dibenzo[bf]thiepin (1) and -oxepin (2) were prepared as stable yellow crystalline compounds, which are the cyclic analogues of electron-donating hexaarylbutadienes. Upon two-electron oxidation, they are reversibly transformed into the title dications (12+ and 22+ ) exhibiting near-infrared (NIR) absorptions, which were also isolated as stable salts. These redox pairs can serve as new entries into less well-explored organic NIR-electrochromic systems, and the separation of redox peaks (electrochemical bistability) was attained for 1/12+ and 2/22+ , thanks to drastic geometrical changes between neutral and dicationic states, as revealed by a series of X-ray analyses. Thiepin-S,S-dioxide analogue (3/32+ ) exhibits quite similar dynamic redox behavior due to nonaromatic nature of the dibenzothiepin and -oxepin unit in 12+ and 22+ , whereas the thiepin-S-oxide derivative (4/42+ ) does not exhibit bistability due to the smaller change in geometry upon electron transfer, showing that a subtle change of a bridging atom in the central seven-membered ring can modify the redox properties.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Chemistry
Journal subject:
QUIMICA
Year:
2022
Document type:
Article
Affiliation country:
Japan