Two new coordination assemblies were prepared by combining the open and close forms of 1,2-bis(5-carboxyl-2-methyl-3-thienyl)perfluorocyclopentene (H 2 dae) with [Mn 2 (saltmen) 2 (H 2 O) 2 ](PF 6 ) 2 , where H 2 saltmen = 2,2′-((1E,1′E)-((2,3-dimethylbutane-2,3-diyl)bis(azaneylylidene)) bis(methaneylylidene))diphenol. From X-ray diffraction analyses, the complexes had the following formula: [Mn 2 (saltmen) 2 (dae-open)] (1 open ) and [Mn(saltmen)(dae-close)]·H 2 O·Et 3 N (1 close ). Both complexes crystallized in the C2/c monoclinic space group. In 1 open , dae-o 2- behaves as a bidentate ligand attached to the outer Mn-saltmen monomer via the oxygen atom of carboxylato groups, whereas in 1 close , the dae-c 2- ligand behaves as a monodentate ligand attached to the external Mn-saltmen dimer by only one carboxylato group of the photochromic ligand. The complexes showed reversible photochromic responses to UV/vis light and showed single-molecule magnet-like behavior. The relaxation times and energy barriers of the metal complexes are clearly affected by UV/vis irradiation.