Spontaneous Symmetry Breaking Facilitates Metal-to-Ligand Charge Transfer: A Quantitative Two-Photon Absorption Study of Ferrocene-phenyleneethynylene Oligomers

Change of the permanent molecular electric dipole moment, Δμ, in a series of nominally centrosymmetric and noncentrosymmteric ferrocene-phenyleneethynylene oligomers was estimated by measuring the two-photon absorption cross-section spectra of the lower energy metal-to-ligand charge-transfer transit...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2018-04, Vol.9 (8), p.1893-1899
Main Authors: Mikhaylov, Alexander, Uudsemaa, Merle, Trummal, Aleksander, Arias, Eduardo, Moggio, Ivana, Ziolo, Ronald, Cooper, Thomas M, Rebane, Aleksander
Format: Article
Language:English
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Summary:Change of the permanent molecular electric dipole moment, Δμ, in a series of nominally centrosymmetric and noncentrosymmteric ferrocene-phenyleneethynylene oligomers was estimated by measuring the two-photon absorption cross-section spectra of the lower energy metal-to-ligand charge-transfer transitions using femtosecond nonlinear transmission method and was found to vary in the range up to 12 D, with the highest value corresponding to the most nonsymmetric system. Calculations of the Δμ performed by the TD-DFT method show quantitative agreement with the experimental values and reveal that facile rotation of the ferrocene moieties relative to the organic ligand breaks the ground-state inversion symmetry in the nominally symmetric structures.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.8b00525