Analysis of the photomagnetic properties of cyano-bridged heterobimetallic complexes by X-ray diffraction

Helle Svendsen, Mads Ry Vogel Jørgensen, Jacob Overgaard, Yu Sheng Chen, Guillaume Chastanet, Jean François Létard, Kenichi Kato, Masaki Takata, Bo B. Iversen

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)10974-10984
Number of pages11
JournalInorganic chemistry
Volume50
Issue number21
DOIs
Publication statusPublished - 2011 Nov 7
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Analysis of the photomagnetic properties of cyano-bridged heterobimetallic complexes by X-ray diffraction'. Together they form a unique fingerprint.

Cite this