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Ligand-field excited states of hexacyanochromate and hexacyanocobaltate as sensitisers for near-infrared luminescence from Nd(iii) and Yb(iii) in cyanide-bridged d–f assemblies

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Abstract

Crystallisation of [Co(CN)6]3− or [Cr(CN)6]3− with Ln(iii) salts (Ln = Nd, Gd, Yb) from aqueous dmf afforded the cyanide-bridged d/f systems [Ln(dmf)4(H2O)3(μ-CN)Co(CN)5] (Co–Ln, discrete dinuclear species) and [Cr(CN)4(μ-CN)2Ln(H2O)2(dmf)4]∞ (Cr–Ln, infinite cyanide-bridged chains with alternating Cr and Ln centres). With Ln = Gd the characteristic long-lived phosphorescence from d–d excited states of the [M(CN)6]3− units was apparent in the red region of the spectrum, with lifetimes of the order of 1 μs, since the heavy atom effect of the Gd(iii) promotes inter-system crossing at the [M(CN)6]3− units to generate the phosphorescent spin-forbidden excited states. With Ln = Yb or Nd however, the d-block luminescence was completely quenched due to fast (>108 s−1) energy-transfer to the Ln(iii) centre, resulting in the characteristic sensitised emission from Yb(iii) and Nd(iii) in the near-IR region. For both Co–Nd and Co–Yb, calculations based on spectroscopic overlap between emission of the donor (Co) and absorption of the acceptor (Ln) suggest that the Dexter energy-transfer mechanism is responsible for the complete quenching that we observe.

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Authors and Affiliations

  1. Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, England

    Theodore Lazarides, Graham M. Davies, Harry Adams & Michael D. Ward

  2. Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche (ISOF-CNR), Via P. Gobetti 101, 40129, Bologna, Italy

    Cristiana Sabatini, Francesco Barigelletti & Andrea Barbieri

  3. Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, England

    Stephen Faulkner

  4. School of Chemistry, Main Building, Cardiff University, Cardiff, CF10 3AT, England

    Simon J. A. Pope

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  1. Theodore Lazarides
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Lazarides, T., Davies, G.M., Adams, H. et al. Ligand-field excited states of hexacyanochromate and hexacyanocobaltate as sensitisers for near-infrared luminescence from Nd(iii) and Yb(iii) in cyanide-bridged d–f assemblies. Photochem Photobiol Sci 6, 1152–1157 (2007). https://doi.org/10.1039/b708683k

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