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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
und Weigand, Jan J.
(2023)
Visible‐Light‐Triggered Photoswitching of Diphosphene Complexes.
Angewandte Chemie, e202306706.
Veröffentlichungsdatum dieses Volltextes: 09 Nov 2023 17:50
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.54960
Zusammenfassung
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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| Dokumentenart | Artikel | ||||
| Titel eines Journals oder einer Zeitschrift | Angewandte Chemie | ||||
| Verlag: | Wiley | ||||
|---|---|---|---|---|---|
| Seitenbereich: | e202306706 | ||||
| Datum | 6 September 2023 | ||||
| Institutionen | Chemie und Pharmazie > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf | ||||
| Identifikationsnummer |
| ||||
| Stichwörter / Keywords | Diphosphenes · Photoisomerization · Photoswitch · Quantum Chemical Calculations · Structure Elucidation | ||||
| Dewey-Dezimal-Klassifikation | 500 Naturwissenschaften und Mathematik > 500 Naturwissenschaften 500 Naturwissenschaften und Mathematik > 540 Chemie | ||||
| Status | Veröffentlicht | ||||
| Begutachtet | Ja, diese Version wurde begutachtet | ||||
| An der Universität Regensburg entstanden | Zum Teil | ||||
| URN der UB Regensburg | urn:nbn:de:bvb:355-epub-549608 | ||||
| Dokumenten-ID | 54960 |
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