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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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
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cited_by cdi_FETCH-LOGICAL-a345t-8485304e07134c555516685ef6985f25879075fd75c5e16409fbddeb0a4a35423
cites cdi_FETCH-LOGICAL-a345t-8485304e07134c555516685ef6985f25879075fd75c5e16409fbddeb0a4a35423
container_end_page 1899
container_issue 8
container_start_page 1893
container_title The journal of physical chemistry letters
container_volume 9
creator Mikhaylov, Alexander
Uudsemaa, Merle
Trummal, Aleksander
Arias, Eduardo
Moggio, Ivana
Ziolo, Ronald
Cooper, Thomas M
Rebane, Aleksander
description 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.
doi_str_mv 10.1021/acs.jpclett.8b00525
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title Spontaneous Symmetry Breaking Facilitates Metal-to-Ligand Charge Transfer: A Quantitative Two-Photon Absorption Study of Ferrocene-phenyleneethynylene Oligomers
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