Near-Infrared Electrochromic Behavior of Dibenzothiepin Derivatives Attached with Two Michler's Hydrol Blue Units

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.