Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy: 4f orbital contribution in the metal-ligand interaction
Natsuki Hosoya, Keizo Yada, Tomohide Masuda, Erika Nakajo, Satoshi Yabushita, Atsushi Nakajima
The electronic structures of lanthanide (Ln) ions sandwiched between 1,3,5,7-cyclooctatetraene (COT), Ln(COT)2-, have been investigated by anion photoelectron spectroscopy. Complexes of 12 Ln atoms were investigated (excluding promethium (Pm), europium (Eu), and ytterbium (Yb)). The 213 nm photoelectron (PE) spectra of Ln(COT)2- exhibit two peaks assignable to the highest occupied molecular orbital (HOMO; e 2u) and the next HOMO (HOMO-1; e2g) approximately at 2.6 and 3.6 eV, respectively, and their energy gap increases as the central metal atom progresses from lanthanum (La) to lutetium (Lu). Since lanthanide contraction shortens the distance between the Ln atom and the COT ligands, the widening energy gap represents the destabilization of the e2u orbital as well as the stabilization of the e2g orbital. Evidence for 4f orbital contribution in the metal-ligand interaction has been revealed by the Ln atom dependence in which the same e2u orbital symmetry enables an interaction between the 4f orbital of Ln atoms and the π orbital of COT.
https://doi.org/10.1021/jp411660e
Published - 2014 May 1
10.1021/jp411660e
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ligands Physics & Astronomy 100%
Photoelectron Spectroscopy Chemical Compounds 97%
anions Physics & Astronomy 93%
Orbital Chemical Compounds 82%
photoelectron spectroscopy Physics & Astronomy 81%
Lanthanoid Atom Chemical Compounds 74%
electronic structure Physics & Astronomy 74%
Electronic State Chemical Compounds 72%
Hosoya, N., Yada, K., Masuda, T., Nakajo, E., Yabushita, S., & Nakajima, A. (2014). Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy: 4f orbital contribution in the metal-ligand interaction. Journal of Physical Chemistry A, 118(17), 3051-3060. https://doi.org/10.1021/jp411660e
Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy : 4f orbital contribution in the metal-ligand interaction. / Hosoya, Natsuki; Yada, Keizo; Masuda, Tomohide et al.
In: Journal of Physical Chemistry A, Vol. 118, No. 17, 01.05.2014, p. 3051-3060.
Hosoya, N, Yada, K, Masuda, T, Nakajo, E, Yabushita, S & Nakajima, A 2014, 'Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy: 4f orbital contribution in the metal-ligand interaction', Journal of Physical Chemistry A, vol. 118, no. 17, pp. 3051-3060. https://doi.org/10.1021/jp411660e
Hosoya N, Yada K, Masuda T, Nakajo E, Yabushita S, Nakajima A. Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy: 4f orbital contribution in the metal-ligand interaction. Journal of Physical Chemistry A. 2014 May 1;118(17):3051-3060. doi: 10.1021/jp411660e
Hosoya, Natsuki ; Yada, Keizo ; Masuda, Tomohide et al. / Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy : 4f orbital contribution in the metal-ligand interaction. In: Journal of Physical Chemistry A. 2014 ; Vol. 118, No. 17. pp. 3051-3060.
@article{b3825089d22b44909d5223038afb7460,
title = "Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy: 4f orbital contribution in the metal-ligand interaction",
abstract = "The electronic structures of lanthanide (Ln) ions sandwiched between 1,3,5,7-cyclooctatetraene (COT), Ln(COT)2-, have been investigated by anion photoelectron spectroscopy. Complexes of 12 Ln atoms were investigated (excluding promethium (Pm), europium (Eu), and ytterbium (Yb)). The 213 nm photoelectron (PE) spectra of Ln(COT)2- exhibit two peaks assignable to the highest occupied molecular orbital (HOMO; e 2u) and the next HOMO (HOMO-1; e2g) approximately at 2.6 and 3.6 eV, respectively, and their energy gap increases as the central metal atom progresses from lanthanum (La) to lutetium (Lu). Since lanthanide contraction shortens the distance between the Ln atom and the COT ligands, the widening energy gap represents the destabilization of the e2u orbital as well as the stabilization of the e2g orbital. Evidence for 4f orbital contribution in the metal-ligand interaction has been revealed by the Ln atom dependence in which the same e2u orbital symmetry enables an interaction between the 4f orbital of Ln atoms and the π orbital of COT.",
author = "Natsuki Hosoya and Keizo Yada and Tomohide Masuda and Erika Nakajo and Satoshi Yabushita and Atsushi Nakajima",
doi = "10.1021/jp411660e",
journal = "Journal of Physical Chemistry A",
T1 - Investigation of the electronic structures of organolanthanide sandwich complex anions by photoelectron spectroscopy
T2 - 4f orbital contribution in the metal-ligand interaction
AU - Hosoya, Natsuki
AU - Yada, Keizo
AU - Masuda, Tomohide
AU - Nakajo, Erika
AU - Yabushita, Satoshi
AU - Nakajima, Atsushi
N2 - The electronic structures of lanthanide (Ln) ions sandwiched between 1,3,5,7-cyclooctatetraene (COT), Ln(COT)2-, have been investigated by anion photoelectron spectroscopy. Complexes of 12 Ln atoms were investigated (excluding promethium (Pm), europium (Eu), and ytterbium (Yb)). The 213 nm photoelectron (PE) spectra of Ln(COT)2- exhibit two peaks assignable to the highest occupied molecular orbital (HOMO; e 2u) and the next HOMO (HOMO-1; e2g) approximately at 2.6 and 3.6 eV, respectively, and their energy gap increases as the central metal atom progresses from lanthanum (La) to lutetium (Lu). Since lanthanide contraction shortens the distance between the Ln atom and the COT ligands, the widening energy gap represents the destabilization of the e2u orbital as well as the stabilization of the e2g orbital. Evidence for 4f orbital contribution in the metal-ligand interaction has been revealed by the Ln atom dependence in which the same e2u orbital symmetry enables an interaction between the 4f orbital of Ln atoms and the π orbital of COT.
AB - The electronic structures of lanthanide (Ln) ions sandwiched between 1,3,5,7-cyclooctatetraene (COT), Ln(COT)2-, have been investigated by anion photoelectron spectroscopy. Complexes of 12 Ln atoms were investigated (excluding promethium (Pm), europium (Eu), and ytterbium (Yb)). The 213 nm photoelectron (PE) spectra of Ln(COT)2- exhibit two peaks assignable to the highest occupied molecular orbital (HOMO; e 2u) and the next HOMO (HOMO-1; e2g) approximately at 2.6 and 3.6 eV, respectively, and their energy gap increases as the central metal atom progresses from lanthanum (La) to lutetium (Lu). Since lanthanide contraction shortens the distance between the Ln atom and the COT ligands, the widening energy gap represents the destabilization of the e2u orbital as well as the stabilization of the e2g orbital. Evidence for 4f orbital contribution in the metal-ligand interaction has been revealed by the Ln atom dependence in which the same e2u orbital symmetry enables an interaction between the 4f orbital of Ln atoms and the π orbital of COT.
U2 - 10.1021/jp411660e
DO - 10.1021/jp411660e
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A