Site-Selective Orbital Interactions in an Ultrathin Iron-Carbene Photosensitizer Film

Temperton, Robert H.; Rosemann, Nils W.; Guo, Meiyuan; Johansson, Niclas; Fredin, Lisa A.; Prakash, Om; W�rnmark, Kenneth; Handrup, Karsten; Uhlig, Jens; Schnadt, Joachim; Persson, Petter

Abstract

We present the first experimental study of the frontier orbitals in an ultrathin film of the novel hexa-carbene photosensitizer [Fe(btz)3]3+, where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene). Resonant photoelectron spectroscopy (RPES) was used to probe the electronic structure of films where the molecular and oxidative integrities had been confirmed with optical and X-ray spectroscopies. In combination with density functional theory calculations, RPES measurements provided direct and site-selective information about localization and interactions of occupied and unoccupied molecular orbitals. Fe 2p, N 1s, and C 1s measurements selectively probed the metal, carbene, and side-group contributions revealing strong metal–ligand orbital mixing of the frontier orbitals. This helps explain the remarkable photophysical properties of iron-carbenes in terms of unconventional electronic structure properties and favorable metal–ligand bonding interactions—important for the continued development of these type of complexes toward light-harvesting and light-emitting applications.

Citation

Temperton, R. H., Rosemann, N. W., Guo, M., Johansson, N., Fredin, L. A., Prakash, O., …Persson, P. (2020). Site-Selective Orbital Interactions in an Ultrathin Iron-Carbene Photosensitizer Film. Journal of Physical Chemistry A, 124(8), 1603-1609. https://doi.org/10.1021/acs.jpca.0c00803

• Journal Article Type: Article
• Acceptance Date: Feb 3, 2020
• Online Publication Date: Feb 3, 2020
• Publication Date: Feb 27, 2020
• Deposit Date: Apr 16, 2020
• Publicly Available Date: Apr 16, 2020
• Journal: The Journal of Physical Chemistry A
• Print ISSN: 1089-5639
• Electronic ISSN: 1520-5215
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 124
• Issue: 8
• Pages: 1603-1609
• DOI: https://doi.org/10.1021/acs.jpca.0c00803
• Keywords: Physical and Theoretical Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/4298508
• Publisher URL: https://pubs.acs.org/doi/abs/10.1021/acs.jpca.0c00803