Azobispyrazole Family as Photoswitches Combining (Near‐) Quantitative Bidirectional Isomerization and Widely Tunable Thermal Half‐Lives from Hours to Years**

Azobenzenes are classical molecular photoswitches that have been widely used. In recent endeavors of molecular design, replacing one or both phenyl rings with heteroaromatic rings has emerged as a strategy to expand molecular diversity and access improved photoswitching properties. Many mono-heteroaryl azo molecules with unique structures and/or properties have been developed, but the potential of bis-heteroaryl architectures is far from fully exploited. We report a family of azobispyrazoles, which combine (near-)quantitative bidirectional photoconversion and widely tunable Z-isomer thermal half-lives from hours to years. The two five-membered rings remarkably weaken the intramolecular steric hindrance, providing new possibilities for engineering the geometric and electronic structure of azo photoswitches. Azobispyrazoles generally exhibit twisted Z-isomers that facilitate complete Z→E photoisomerization, and their thermal stability can be broadly adjusted regardless of the twisted shape, overcoming the conflict between photoconversion (favored by the twisted shape) and Z-isomer stability (favored by the orthogonal shape) encountered by mono-heteroaryl azo switches.