We have located links that may give you full text access.
Impact of Diimine Ligand on Singlet-to-Triplet Charge Transfer Electroabsorption in Iron and Ruthenium Complexes.
Journal of Physical Chemistry. A 2024 April 30
The electroabsorption and absorption spectra of eight homoleptic complexes of the general form [M(LL)3 ]2+ where M = Ru, Fe, and LL = 1,10-phenanthroline (phen), 2,2'-bipyridine (bpy), and 4,4',-(R)2 -bpy where R = -OCH3 , -CF3 , were quantified at 77 K in a butyronitrile glass. Intense metal-to-ligand charge transfer (MLCT) absorption bands were evident in the visible region. Electroabsorption spectra measured with applied electric fields >0.2 MV/cm were analyzed by the two-state Liptay model. Significant light-induced dipole moment changes of Δμ⇀ = 4-13 D were found consistent with a metal-to-ligand charge transfer (MLCT) excited state comprised an electron localized on a single diimine ligand, [MIII (LL- )(LL)2 ]*2+ , in the initially formed Franck-Condon excited state. A low energy feature evident in the electroabsorption spectra was assigned to a direct singlet-to-triplet MLCT excited state. The identity of the diimine ligand had an unexpected and large impact on these transitions. Analysis relative to the higher energy absorption provides a comparison of spin-allowed and disallowed transitions for first- and second-row transition metal complexes. With the notable exception of [Fe(CF3 bpy)3 ]2+ , the change in dipole moment for the 3 MLCT excited states was less than or equal to that of the 1 MLCT excited states. The charge transfer distances for the iron complexes were generally larger than those for the Ru complexes, a behavior attributed to a smaller degree of iron-diimine coupling in the ground state. A striking result was the sensitivity of the extinction coefficient and spectral profile of the low energy electroabsorption assigned to the identity of the diimine ligand; data that suggests electronic coupling with ligand localized triplet states and high spin metal centered states must be considered when modeling the Franck-Condon excited state.
Full text links
Related Resources
Trending Papers
Get seemless 1-tap access through your institution/university
For the best experience, use the Read mobile app
All material on this website is protected by copyright, Copyright © 1994-2024 by WebMD LLC.
This website also contains material copyrighted by 3rd parties.
By using this service, you agree to our terms of use and privacy policy.
Your Privacy Choices
You can now claim free CME credits for this literature searchClaim now
Get seemless 1-tap access through your institution/university
For the best experience, use the Read mobile app