Unraveling electronic properties of an organometallic solute: Lippert-Mataga and quantum-chemical extensive study

• Solvatochromism of ligand-to-metal charge-transfer excited states is discussed.
• The change in dipole moment can be obtained with the Lippert-Mataga methodology.
• Quantum-chemical calculations complement the Lippert-Mataga experimental study.

We report a systematic experimental and quantum-chemical study of electric dipole moments of a metal complex, dissolved in organic media, in the ground and electronically-excited states. Electric dipole moments of a model organometallic complex in the ground and emissive states and the difference thereof were analyzed applying simplified Lippert-Mataga methodology and calculations at different levels of density functional theory (B3LYP/DGDZVP, B3LYP/3-21G*, B3LYP/6-31G**, B3LYP/6-311G**, B3LYP/SDD, and B3LYP/cep-121G). The contribution provides the experimental systematic estimation of the change in electric dipole moments of an organometallic solute based on the changes in transition energies induced by systematic variations in the solvent, while the quantum-chemical data complement and detail the spectral results. With the Lippert-Mataga methodology, the existence of general and, to a lesser extent, specific solvent effects was evidenced. The systematic study shed more light on the solvatochromism of organometallic compounds.

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