Efficient solid-state photoswitching of methoxyazobenzene in a metal–organic framework for thermal energy storage

Efficient photoswitching in the solid-state remains rare, yet is highly desirable for the design of functional solid materials. In particular, for molecular solar thermal energy storage materials high conversion to the metastable isomer is crucial to achieve high energy density. Herein, we report that 4-methoxyazobenzene (MOAB) can be occluded into the pores of a metal–organic framework Zn(2)(BDC)(2)(DABCO), where BDC = 1,4-benzenedicarboxylate and DABCO = 1,4-diazabicyclo[2.2.2]octane. The occluded MOAB guest molecules show near-quantitative E → Z photoisomerization under irradiation with 365 nm light. The energy stored within the metastable Z-MOAB molecules can be retrieved as heat during thermally-driven relaxation to the ground-state E-isomer. The energy density of the composite is 101 J g(−1) and the half-life of the Z-isomer is 6 days when stored in the dark at ambient temperature.