Light-Powered Dissipative Assembly of Diazocine Coordination Cages

[Image: see text] Stimuli-responsive coordination cages allow reversible control over guest binding and release, relevant for adaptive receptors, carriers, catalysts, and complex systems. Light serves as an advantageous stimulus, as it can be applied with precise spatial and temporal resolution without producing chemical waste products. We report the first Pd-mediated coordination cage based on ligands embedding a diazocine photoswitch. While the thermodynamically more stable cis-photoisomer sloppily assembles to a mixture of species with general formula [Pd(n)cis-L(2n)], the less stable trans-isomer yields a defined [Pd(2)trans-L(4)] cage that reversibly converts back to the cis-system by irradiation at 530 nm or thermal relaxation. The [Pd(n)cis-L(2n)] species do not bind a given guest; however, [Pd(2)trans-L(4)] is able to encapsulate a bis-sulfonate as long as it is kept assembled, requiring continuous irradiation at 385 nm. In the absence of UV light, thermal relaxation results in back-switching and guest release. Assembly and properties of the system were characterized by a combination of NMR, ion mobility ESI-MS, single-crystal X-ray diffraction, and UV–vis absorption studies.