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Visible‐Light‐Triggered Photoswitching of Diphosphene Complexes
Taube, Clemens, Fidelius, Jannis, Schwedtmann, Kai, Ziegler, Christopher, Kreuter, Florian, Loots, Leigh, Barbour, Leonard J., Tonner‐Zech, Ralf, Wolf, Robert
and Weigand, Jan J.
(2023)
Visible‐Light‐Triggered Photoswitching of Diphosphene Complexes.
Angewandte Chemie, e202306706.
Date of publication of this fulltext: 09 Nov 2023 17:50
Article
DOI to cite this document: 10.5283/epub.54960
Abstract
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-κ2P,κ6C)Mo(CO)2][OTf] (3 a[OTf]), [(2-κ2P,κ6C)Fe(CO)][OTf] ...
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-κ2P,κ6C)Mo(CO)2][OTf] (3 a[OTf]), [(2-κ2P,κ6C)Fe(CO)][OTf] (3 b[OTf]), and [(2-κ2P)Fe(CO)4][OTf] (4[OTf]) were prepared using the triflate salt [(LC)P=P(Dipp)][OTf] (2[OTf) as a precursor (LC=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 η2-diphosphene complexes 3 a,b[OTf] readily undergo isomerization to form blue-colored η1-complexes [(2-κ1P,κ6C)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 (κ2P,κ6C)-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 S1 excited state and proceeds through a conical intersection.
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| Item type | Article | ||||
| Journal or Publication Title | Angewandte Chemie | ||||
| Publisher: | Wiley | ||||
|---|---|---|---|---|---|
| Page Range: | e202306706 | ||||
| Date | 6 September 2023 | ||||
| Institutions | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf | ||||
| Identification Number |
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| Keywords | Diphosphenes · Photoisomerization · Photoswitch · Quantum Chemical Calculations · Structure Elucidation | ||||
| Dewey Decimal Classification | 500 Science > 500 Natural sciences & mathematics 500 Science > 540 Chemistry & allied sciences | ||||
| Status | Published | ||||
| Refereed | Yes, this version has been refereed | ||||
| Created at the University of Regensburg | Partially | ||||
| URN of the UB Regensburg | urn:nbn:de:bvb:355-epub-549608 | ||||
| Item ID | 54960 |
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