The dark side of hydrogen bonds in the design of optical materials: a charge-density perspective.

Abstract

A combined investigation of the structural, electronic, and optical properties of three crystalline nonaaqualanthanoid(III) triflates, [Ln(H2 O)9 (CF3 SO3 )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.

DOI: 10.1002/chem.201300566

Cite this paper

@article{Nelyubina2014TheDS, title={The dark side of hydrogen bonds in the design of optical materials: a charge-density perspective.}, author={Yulia V Nelyubina and Lada N Puntus and Konstantin A Lyssenko}, journal={Chemistry}, year={2014}, volume={20 10}, pages={2860-5} }