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Taube, Clemens ; Fidelius, Jannis ; Schwedtmann, Kai ; Ziegler, Christopher ; Kreuter, Florian ; Loots, Leigh ; Barbour, Leonard J. ; Tonner‐Zech, Ralf ; Wolf, Robert ; Weigand, Jan J.

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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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftAngewandte Chemie
Verlag:Wiley
Seitenbereich:e202306706
Datum6 September 2023
InstitutionenChemie und Pharmazie > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf
Identifikationsnummer
WertTyp
10.1002/ange.202306706DOI
Stichwörter / KeywordsDiphosphenes · Photoisomerization · Photoswitch · Quantum Chemical Calculations · Structure Elucidation
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 500 Naturwissenschaften
500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-549608
Dokumenten-ID54960

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