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The Dark Side of Hydrogen Bonds in the Design of Optical Materials: A Charge-Density Perspective

Authors

  • Dr. Yulia V. Nelyubina,

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    1. A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova Str., 28, Moscow (Russia)
    • A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova Str., 28, Moscow (Russia)

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  • Dr. Lada N. Puntus,

    1. Institute of Radioengineering and Electronics, Russian Academy of Sciences, 125009, Mokhovaya Str., 11-7, Moscow (Russia)
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  • Prof. Konstantin A. Lyssenko

    1. A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova Str., 28, Moscow (Russia)
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Abstract

A combined investigation of the structural, electronic, and optical properties of three crystalline nonaaqualanthanoid(III) triflates, [Ln(H2O)9(CF3SO3)3], has provided unambiguous experimental evidence for charge redistribution in the first coordination sphere of a lanthanide ion as a result of hydrogen bonds with outer-sphere anions. As well as resulting in charge transfer from the noncoordinated anions to the coordinated water molecules, these hydrogen bonds give rise to a new excited state, an hydrogen-bond-induced charge-transfer state, which is observed experimentally for the first time. This state was shown to be responsible for the previously unknown negative aspect of hydrogen bonds with a lanthanide-bound water molecule: rather than increasing the luminescence efficiency of the complex, they can lead to additional quenching that is unfavorable for the task-specific design of optical materials.

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