TY - JOUR
T1 - Analysis of the photomagnetic properties of cyano-bridged heterobimetallic complexes by X-ray diffraction
AU - Svendsen, Helle
AU - Jørgensen, Mads Ry Vogel
AU - Overgaard, Jacob
AU - Chen, Yu Sheng
AU - Chastanet, Guillaume
AU - Létard, Jean François
AU - Kato, Kenichi
AU - Takata, Masaki
AU - Iversen, Bo B.
PY - 2011/11/7
Y1 - 2011/11/7
N2 - Single crystal synchrotron X-ray diffraction measurements have been carried out on [Nd(DMF)4(H2O)3(μ-CN)Fe(CN) 5]•H2O (DMF = dimethyl-formamide), 1; [Y(DMF) 4(H2O)3(μ-CN)Fe(CN)5]•H 2O, 2; [Ce(DMF)4(H2O)3(μ-CN) Fe(CN)5]•H2O, 3; [Sm(DMF)4(H 2O)3(μ-CN)Fe(CN)5]•H2O, 4; [Tb(DMF)4(H2O)3(μ-CN)Fe(CN) 5]•H2O, 5; [Yb(DMF)4(H2O) 3(μ-CN)Fe(CN)5]•H2O, 6; and [Nd(DMF)4(H2O)3(μ-CN)Co(CN) 5]•H2O, 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 K3Fe(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(H2O)3(μ-CN) Fe(CN)5]•H2O, 9, exhibits identical magnetic responses in the UV-induced excited crystal structure.
AB - Single crystal synchrotron X-ray diffraction measurements have been carried out on [Nd(DMF)4(H2O)3(μ-CN)Fe(CN) 5]•H2O (DMF = dimethyl-formamide), 1; [Y(DMF) 4(H2O)3(μ-CN)Fe(CN)5]•H 2O, 2; [Ce(DMF)4(H2O)3(μ-CN) Fe(CN)5]•H2O, 3; [Sm(DMF)4(H 2O)3(μ-CN)Fe(CN)5]•H2O, 4; [Tb(DMF)4(H2O)3(μ-CN)Fe(CN) 5]•H2O, 5; [Yb(DMF)4(H2O) 3(μ-CN)Fe(CN)5]•H2O, 6; and [Nd(DMF)4(H2O)3(μ-CN)Co(CN) 5]•H2O, 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 K3Fe(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(H2O)3(μ-CN) Fe(CN)5]•H2O, 9, exhibits identical magnetic responses in the UV-induced excited crystal structure.
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U2 - 10.1021/ic2015258
DO - 10.1021/ic2015258
M3 - Article
C2 - 21985223
AN - SCOPUS:80155151960
SN - 0020-1669
VL - 50
SP - 10974
EP - 10984
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -