Single crystal synchrotron X-ray diffraction measurements have been carried out on [Nd(DMF)(4)(H(2)O)(3)(μ-CN)Fe(CN)(5)]*H(2)O (DMF = dimethyl-formamide), 1; [Y(DMF)(4)(H(2)O)(3)(μ-CN)Fe(CN)(5)]*H(2)O, 2; [Ce(DMF)(4)(H(2)O)(3)(μ-CN)Fe(CN)(5)]*H(2)O, 3; [Sm(DMF)(4)(H(2)O)(3)(μ-CN)Fe(CN)(5)]*H(2)O, 4; [Tb(DMF)(4)(H(2)O)(3)(μ-CN)Fe(CN)(5)]*H(2)O, 5; [Yb(DMF)(4)(H(2)O)(3)(μ-CN)Fe(CN)(5)]*H(2)O, 6; and [Nd(DMF)(4)(H(2)O)(3)(μ-CN)Co(CN)(5)]*H(2)O, 7, at 15(2) K with and without UV illumination of the crystals. Significant changes in unit cell parameters are observed for all of the iron-containing complexes, while compound 7 shows no response to UV illumination. These results are consistent with previous results and are furthermore reproduced by powder synchrotron X-ray diffraction for compounds 1 and 7. Photoexcited crystal structures have been determined for 1-6 from refinements of two-conformer models, and excited state occupancies in the range 80-94% are found. Significant bond length changes are observed for the Fe-ligand bonds (up to 0.06 Å), the cyano bonds (up to 0.02 Å), and the lanthanide-ligand bonds (up to 0.1 Å). On the contrary, powder X-ray diffraction on the simple compound K(3)Fe(CN)(6), 8, upon UV illumination does not show any structural changes, suggesting that the photomagnetic effect requires the presence of both the transition metal and the lanthanide ion. Photomagnetic measurements show an increase in magnetization of the excited state of 1 of up to 3%, which is much diminished compared with previously published values of 45%. Furthermore, they show that the isostructural complex [La(DMF)(4)(H(2)O)(3)(μ-CN)Fe(CN)(5)]*H(2)O, 9, exhibits identical magnetic responses in the UV-induced excited crystal structure.< Réduire