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Towards Noble-Metal-Free Dyads : Ground and Excited State Tuning by a Cobalt Dimethylglyoxime Motif Connected to an Iron N-Heterocyclic Carbene Photosensitizer

Zimmer, Peter; Burkhardt, Lukas; Schepper, Rahel; Zheng, Kaibo LU ; Gosztola, David; Neuba, Adam; Flörke, Ulrich; Wölper, Christoph; Schoch, Roland and Gawelda, Wojciech, et al. (2018) In European Journal of Inorganic Chemistry 2018(48). p.5203-5214
Abstract

Heteroleptic iron based complexes bearing the 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine motif and a polypridine ligand have been synthesized and characterized in their ground and excited state. This series of complexes includes a first example of a hetero-bimetallic complex connecting an iron N-heterocyclic carbene photosensitizer with a cobalt dimethylglyoxime fragment. Focus is set on the influence of the linker and cobalt center as second ligand at the iron center on the photophysics. While electronic absorption spectroscopy and cyclic voltammetry reveal a weak mutual influence of the single ligands in the heteroleptic complexes, an increasing MLCT lifetime with larger π-accepting abilities was found by... (More)

Heteroleptic iron based complexes bearing the 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine motif and a polypridine ligand have been synthesized and characterized in their ground and excited state. This series of complexes includes a first example of a hetero-bimetallic complex connecting an iron N-heterocyclic carbene photosensitizer with a cobalt dimethylglyoxime fragment. Focus is set on the influence of the linker and cobalt center as second ligand at the iron center on the photophysics. While electronic absorption spectroscopy and cyclic voltammetry reveal a weak mutual influence of the single ligands in the heteroleptic complexes, an increasing MLCT lifetime with larger π-accepting abilities was found by time-resolved transient absorption spectroscopy, with maximum lifetime in the case of the hetero-bimetallic dyad. Concurrently the MC lifetimes were observed to decrease. The reported results will allow to develop guidelines for designing bimetallic devices, which may allow electron transfer from the photosensitizer fragment to a catalytically active center.

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organization
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type
Contribution to journal
publication status
published
subject
keywords
Cobalt, Dyad, Iron, Iron complexes, Photochemistry
in
European Journal of Inorganic Chemistry
volume
2018
issue
48
pages
12 pages
publisher
John Wiley & Sons
external identifiers
  • scopus:85058715058
ISSN
1434-1948
DOI
10.1002/ejic.201800946
language
English
LU publication?
yes
id
da6aac3c-c509-40e5-ae94-5c4566676193
date added to LUP
2019-01-14 11:28:30
date last changed
2019-02-20 11:42:47
@article{da6aac3c-c509-40e5-ae94-5c4566676193,
  abstract     = {<p>Heteroleptic iron based complexes bearing the 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine motif and a polypridine ligand have been synthesized and characterized in their ground and excited state. This series of complexes includes a first example of a hetero-bimetallic complex connecting an iron N-heterocyclic carbene photosensitizer with a cobalt dimethylglyoxime fragment. Focus is set on the influence of the linker and cobalt center as second ligand at the iron center on the photophysics. While electronic absorption spectroscopy and cyclic voltammetry reveal a weak mutual influence of the single ligands in the heteroleptic complexes, an increasing MLCT lifetime with larger π-accepting abilities was found by time-resolved transient absorption spectroscopy, with maximum lifetime in the case of the hetero-bimetallic dyad. Concurrently the MC lifetimes were observed to decrease. The reported results will allow to develop guidelines for designing bimetallic devices, which may allow electron transfer from the photosensitizer fragment to a catalytically active center.</p>},
  author       = {Zimmer, Peter and Burkhardt, Lukas and Schepper, Rahel and Zheng, Kaibo and Gosztola, David and Neuba, Adam and Flörke, Ulrich and Wölper, Christoph and Schoch, Roland and Gawelda, Wojciech and Canton, Sophie E. and Bauer, Matthias},
  issn         = {1434-1948},
  keyword      = {Cobalt,Dyad,Iron,Iron complexes,Photochemistry},
  language     = {eng},
  month        = {12},
  number       = {48},
  pages        = {5203--5214},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Towards Noble-Metal-Free Dyads : Ground and Excited State Tuning by a Cobalt Dimethylglyoxime Motif Connected to an Iron N-Heterocyclic Carbene Photosensitizer},
  url          = {http://dx.doi.org/10.1002/ejic.201800946},
  volume       = {2018},
  year         = {2018},
}