Visible‐Light‐Triggered Photoswitching of Diphosphene Complexes Article Swipe
Clemens Taube
,
Jannis Fidelius
,
Kai Schwedtmann
,
Christopher J. Ziegler
,
Florian Kreuter
,
Leigh Loots
,
Leonard J. Barbour
,
Ralf Tonner
,
Robert Wolf
,
Jan J. Weigand
·
YOU?
·
· 2023
· Open Access
·
· DOI: https://doi.org/10.1002/anie.202306706
YOU?
·
· 2023
· Open Access
·
· DOI: https://doi.org/10.1002/anie.202306706
Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [( 2 ‐κ 2 P, κ 6 C)Mo(CO) 2 ][OTf] ( 3 a [OTf]), [( 2 ‐κ 2 P, κ 6 C)Fe(CO)][OTf] ( 3 b [OTf]), and [( 2 ‐κ 2 P)Fe(CO) 4 ][OTf] ( 4 [OTf]) were prepared using the triflate salt [(L C )P=P(Dipp)][OTf] ( 2 [OTf) as a precursor (L C =4,5‐dichloro‐1,3‐bis(2,6‐diisiopropylphenyl)‐imidazolin‐2‐yl; Dipp=2,6‐diisiopropylphenyl, OTf=triflate). Upon exposure to blue or UV light (λ=400 nm, 470 nm), the initially red‐colored η 2 ‐diphosphene complexes 3 a , b [OTf] readily undergo isomerization to form blue‐colored η 1 ‐complexes [( 2 ‐κ 1 P, κ 6 C)M(CO) n ][OTf] ( 5 a , b [OTf]; a : M=Mo, n=2; b : M=Fe, n=1). This haptotropic rearrangement is reversible, and the ( κ 2 P, κ 6 C)‐coordination mode gradually reverts back upon dissolution in coordinating solvents or more rapidly upon exposure to yellow or red irradiation (λ=590 nm, 630 nm). The electronic reasons for the reversible visible‐light‐induced photoswitching observed for 3 a , b [OTf] are elucidated by DFT calculations. These calculations indicate that the photochromic isomerization originates from the S 1 excited state and proceeds through a conical intersection.
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- Type
- article
- Language
- en
- Landing Page
- https://doi.org/10.1002/anie.202306706
- OA Status
- green
- Cited By
- 19
- References
- 47
- Related Works
- 10
- OpenAlex ID
- https://openalex.org/W4386467561
All OpenAlex metadata
Raw OpenAlex JSON
- OpenAlex ID
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https://openalex.org/W4386467561Canonical identifier for this work in OpenAlex
- DOI
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https://doi.org/10.1002/anie.202306706Digital Object Identifier
- Title
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Visible‐Light‐Triggered Photoswitching of Diphosphene ComplexesWork title
- Type
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articleOpenAlex work type
- Language
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enPrimary language
- Publication year
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2023Year of publication
- Publication date
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2023-09-06Full publication date if available
- Authors
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Clemens Taube, Jannis Fidelius, Kai Schwedtmann, Christopher J. Ziegler, Florian Kreuter, Leigh Loots, Leonard J. Barbour, Ralf Tonner, Robert Wolf, Jan J. WeigandList of authors in order
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https://doi.org/10.1002/anie.202306706Publisher landing page
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YesWhether a free full text is available
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greenOpen access status per OpenAlex
- OA URL
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https://doi.org/10.5283/epub.54960Direct OA link when available
- Concepts
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Isomerization, Trifluoromethanesulfonate, Chemistry, Photochemistry, Photochromism, Photoisomerization, Irradiation, Excited state, Stereochemistry, Crystallography, Medicinal chemistry, Catalysis, Organic chemistry, Nuclear physics, PhysicsTop concepts (fields/topics) attached by OpenAlex
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19Total citation count in OpenAlex
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2025: 9, 2024: 8, 2023: 2Per-year citation counts (last 5 years)
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47Number of works referenced by this work
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10Other works algorithmically related by OpenAlex
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