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A photoswitchable ligand and palladium(II) ions form a dynamic mixture of self‐assembled metallosupramolecular structures. The photoswitching ligand is an ortho‐fluoroazobenzene with appended pyridyl groups. Combining the E‐isomer with palladium(II) salts affords a double‐walled triangle with composition [Pd3L6]6+ and a distorted tetrahedron [Pd4L8]8+ (1 : 2 ratio at 298 K). Irradiation with 410 nm...
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