Peri‐Anthracenethioindigo: A Scaffold for Efficient All‐Red‐Light and Near‐Infrared Molecular Photoswitching.

Molecular photoswitching with red light is greatly desired to evade photodamage and achieve specific photoresponses. In virtually all reported cases however, only one switching direction uses red light while for the reverse switching, UV or visible light is needed. All‐red‐light photoswitching brings with it the clear advantage of pushing photoswitching to the limit of the low‐energy spectrum, but no viable system is available currently. Here we report on peri‐anthracenethioindigo (PAT) as molecular scaffold for highly efficient all‐red‐light photoswitching with an outstanding performance and property profile. The PAT photoswitch provides near‐infrared (NIR) absorption up to 850 nm, large negative photochromism with more than 140 nm maxima shifts and changes color from green to blue upon irradiation with two shades of red light. Thermal stability of the metastable Z isomer is high with a corresponding half‐life of days at 20 °C. Application in red‐light responsive polymers undergoing pronounced and reversible green to blue color changes demonstrate spatially resolved photoswitching. The PAT photoswitch thus offers unique responsiveness to very low energy light together with predictable and large geometrical changes within a rigid molecular scaffold. We expect a plethora of applications for PAT in the near future, e.g. in materials, molecular machines or biological context. [ABSTRACT FROM AUTHOR]