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Experimental and DFT/Time-Dependent DFT Studies on Neutral and One-Electron-Reduced Quinoxaline and Pyrazine Precursors and Their Mononuclear (PdII, PtII) Derivatives

Authors

  • Maria Pia Donzello,

    Corresponding author
    1. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy
    • Maria Pia Donzello, Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy===

      Enrico Bodo, Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy===

      Karl M. Kadish, Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA===

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  • Giorgia De Mori,

    1. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy
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  • Elisa Viola,

    1. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy
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  • David Futur,

    1. Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA
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  • Zhen Fu,

    1. Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA
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  • Corrado Rizzoli,

    1. Dipartimento di Chimica, Università di Parma, Viale G. P. Usberti 17-A, 43124 Parma, Italy
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  • Luisa Mannina,

    1. Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy
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  • Enrico Bodo,

    Corresponding author
    1. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy
    • Maria Pia Donzello, Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy===

      Enrico Bodo, Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy===

      Karl M. Kadish, Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA===

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  • Maria Luisa Astolfi,

    1. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy
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  • Claudio Ercolani,

    1. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy
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  • Karl M. Kadish

    Corresponding author
    1. Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA
    • Maria Pia Donzello, Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy===

      Enrico Bodo, Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome, Italy===

      Karl M. Kadish, Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA===

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Abstract

Electrochemical and UV/Vis spectral studies on the quinoxaline compound 2,3-di(2-pyridyl)-6,7-dicyano-1,4-quinoxaline, [(CN)2Py2Qx], its metallated derivatives [(CN)2Py2QxMCl2] (M = PdII, PtII) and their analogues sharing the dicyanopyrazine fragment are presented and discussed. X-ray work on the new quinoxaline complex [(CN)2Py2QxPtCl2] establishes that PtII is coordinated to the pyridine N atoms (“py–py” coordination). The spectra of the 1– charged quinoxaline and pyrazine compounds show new intense absorptions in the region of 500–900 nm, and redshifted bands in the 250–400 nm region. By using DFT/time-dependent DFT calculations, the spin density and spectral features of both couples of precursors and PtII derivatives were investigated in terms of single-electron excitations between the Kohn–Sham orbitals of the optimized structures in the gas and condensed phases. A detailed comparison is allowed of the experimental and calculated spectral features of the neutral and 1– charged species.

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