Investigation of the Electronic Structures of Organolanthanide Sandwich Complex Anions by Photoelectron Spectroscopy: 4f Orbital Contribution in the Metal–Ligand Interaction

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 photoele...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-05, Vol.118 (17), p.3051-3060
Main Authors: Hosoya, Natsuki, Yada, Keizo, Masuda, Tomohide, Nakajo, Erika, Yabushita, Satoshi, Nakajima, Atsushi
Format: Article
Language:English
Subjects:
Anions
Atomic properties
Electronic structure
Energy gap
Lanthanides
Molecular orbitals
Orbitals
Photoelectron spectroscopy
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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; e2u) 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.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp411660e