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Structure of cyano-bridged Eu(III)—Co(III) bimetallic assembly and its application to photophysical verification of photomagnetic phenomenon

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Abstract

New crystal structure of Eu(DMF)4(H2O)3Co(CN)6·H2O (DMF = N,N′-dimethylformamide) (Eu-Co) has been determined to be monoclinic, P2(1)/n, a = 19.796(12) Å, b = 8.862(11) Å, c = 17.525(10) Å, β = 96.26(5)°, V = 3056(5) Å3, Z = 4. The Eu(III) ion adopts an antiprismatic eight-coordination and forms a cyano bridge with r(Eu-N) = 2.496(7) Å and Θ(Eu-N-C) = 165.7(7)° to the Co(III) ion. The complex exhibits some common features with the Eu-Fe complex. Diffuse reflectance electronic spectra and magnetic susceptibility of Eu-Cr, Eu-Mn, Eu-Fe, and Eu-Co complexes were compared. By substituting the metal ions, both electronic and structural features affected the charge transfer bands and superexchange interactions concerning cyanide ligands. In addition, only Eu-Co exhibited 5 D 0 → 7 F 2 and 5 D 0 → 7 F 1 luminescence bands at 16300 cm−1 and 16900 cm−1, respectively at 298 K (λex = 360 nm (27000 cm−1)), because quenching by cyano-bridged ions did not prevent Eu(III) ion from exhibiting emission. Thus, only Eu-Co may be suitable for verification of an assumption of mechanism concerning drastic photoinduced magnetic changes for Nd-Fe. Merely small decrease of magnetization was observed for Eu-Co after UV light irradiation at 2.0 K. This result was attributed to slight structural changes around cyano bridges without transitions of spin states.

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  1. Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, 223-8522, Japan

    T. Akitsu & Y. Einaga

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  1. T. Akitsu
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  2. Y. Einaga
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Correspondence to T. Akitsu.

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Akitsu, T., Einaga, Y. Structure of cyano-bridged Eu(III)—Co(III) bimetallic assembly and its application to photophysical verification of photomagnetic phenomenon. Chem. Pap. 61, 194–198 (2007). https://doi.org/10.2478/s11696-007-0019-2

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  • DOI: https://doi.org/10.2478/s11696-007-0019-2

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