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)(H2O)(2)](PF6)(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)]center dot H2O center dot Et3N (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.