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Gold(I) Formamidinate Clusters: The Structure, Luminescence, and Electrochemistry of the Tetranuclear, Base-Free [Au4(ArNC(H)NAr)4]

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Abstract

The structures of the tetragold(I) formamidinate cluster complexes, [Au4(ArNC(H)NAr)4], Ar=C6H4-4-OMe (1), C6H3-3,5-Cl (2), C6H4-4-Me (3), have been characterized by x-ray crystallography. The range of Au⋅⋅⋅Au distances is 2.8–3.0 Å. The angles at Au⋅⋅⋅Au⋅⋅⋅Au are acute and obtuse 70 and 109°, 88 and 91°, and 63 and 116° in 1, 2, and 3, respectively. The four gold atoms are located at the corner of a rhomboid with the formamidinate ligands bridged above and below the near plane of the four Au(I) atoms. The tetranuclear gold(I) complexes show a bright blue-green luminescence under UV light, with an emission at ∼490 nm and a weak emission at ∼530 nm in the solid state, at room temp and 77 K. The oxidation of the formamidinate cluster, 1, has been studied electrochemically in 0.1 M Bu4NPF6/CH2Cl2 at a Pt working electrode with different scan rates. Three waves were obtained, 0.75, 0.95, and 1.09V vs. Ag/AgCl at a scan rate of 500 mV/s, the three waves are reversible. The potentials are independent of the scan rate in the range 50 mV/s to 3 V/s. The current at the third wave is larger than those at the first two.

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Authors and Affiliations

  1. Laboratory for Molecular Structure and Bonding, Department of Chemistry, Texas A&M University, College Station, Texas, 77843-3255

    Ahmed A. Mohamed, Hanan E. Abdou, Michael D. Irwin & John P. Fackler Jr.

  2. Departamento de Química, Grupo de Síntesis Química de La Rioja, UA-CSIC, Universidad de la Rioja, Madre de Dios 51, E-26006, Logroño, Spain

    José M. López-de-Luzuriaga

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  1. Ahmed A. Mohamed
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  2. Hanan E. Abdou
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  4. José M. López-de-Luzuriaga
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  5. John P. Fackler Jr.
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Mohamed, A.A., Abdou, H.E., Irwin, M.D. et al. Gold(I) Formamidinate Clusters: The Structure, Luminescence, and Electrochemistry of the Tetranuclear, Base-Free [Au4(ArNC(H)NAr)4]. Journal of Cluster Science 14, 253–266 (2003). https://doi.org/10.1023/B:JOCL.0000005062.20754.5f

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  • DOI: https://doi.org/10.1023/B:JOCL.0000005062.20754.5f

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