Co‐Harvest Phase‐Change Enthalpy and Isomerization Energy for High‐Energy Heat Output by Controlling Crystallization of Alkyl‐Grafted Azobenzene Molecules

Photoisomerization‐induced phase change are important for co‐harvesting the latent heat and isomerization energy of azobenzene molecules. Chemically optimizing heat output and energy delivery at alternating temperatures are challenging because of the differences in crystallizability and isomerization. This article reports two series of asymmetrically alkyl‐grafted azobenzene (Azo‐g), with and without a methyl group, that have an optically triggered phase change. Three exothermic modes were designed to utilize crystallization enthalpy (∆ H c ) and photothermal (isomerization) energy (∆ H p ) at different temperatures determined by the crystallization. Azo‐g has high heat output (275–303 J g −1 ) by synchronously releasing ∆ H c and ∆ H p over a wide temperature range (−79 °C to 25 °C). We fabricated a new distributed energy utilization and delivery system to realize a temperature increase of 6.6 °C at a temperature of −8 °C. The findings offer insight into selective utilization of latent heat and isomerization energy by molecular optimization of crystallization and isomerization processes.