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

Temperton, Robert H. ; Rosemann, Nils W. LU ; Guo, Meiyuan ; Johansson, Niclas LU ; Fredin, Lisa A. LU ; Prakash, Om LU ; Wärnmark, Kenneth LU ; Handrup, Karsten LU ; Uhlig, Jens LU and Schnadt, Joachim LU orcid , et al. (2020) In Journal of Physical Chemistry A 124(8). p.1603-1609
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... (More)

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.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry A
volume
124
issue
8
pages
7 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:32011141
  • scopus:85081160642
ISSN
1089-5639
DOI
10.1021/acs.jpca.0c00803
language
English
LU publication?
yes
id
dd728783-da22-48a2-9dee-18c3b8e919a7
date added to LUP
2020-04-02 17:27:46
date last changed
2025-05-16 23:36:33
@article{dd728783-da22-48a2-9dee-18c3b8e919a7,
  abstract     = {{<p>We present the first experimental study of the frontier orbitals in an ultrathin film of the novel hexa-carbene photosensitizer [Fe(btz)<sub>3</sub>]<sup>3+</sup>, 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.</p>}},
  author       = {{Temperton, Robert H. and Rosemann, Nils W. and Guo, Meiyuan and Johansson, Niclas and Fredin, Lisa A. and Prakash, Om and Wärnmark, Kenneth and Handrup, Karsten and Uhlig, Jens and Schnadt, Joachim and Persson, Petter}},
  issn         = {{1089-5639}},
  language     = {{eng}},
  month        = {{02}},
  number       = {{8}},
  pages        = {{1603--1609}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Physical Chemistry A}},
  title        = {{Site-Selective Orbital Interactions in an Ultrathin Iron-Carbene Photosensitizer Film}},
  url          = {{http://dx.doi.org/10.1021/acs.jpca.0c00803}},
  doi          = {{10.1021/acs.jpca.0c00803}},
  volume       = {{124}},
  year         = {{2020}},
}