Visible-Light-Triggered Photoswitching of Diphosphene Complexes
Publikation: Beitrag in Fachzeitschrift › Forschungsartikel › Beigetragen › Begutachtung
Beitragende
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] (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.
Details
Originalsprache | Englisch |
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Aufsatznummer | e202306706 |
Fachzeitschrift | Angewandte Chemie - International Edition |
Jahrgang | 62 |
Ausgabenummer | 47 |
Publikationsstatus | Veröffentlicht - 20 Nov. 2023 |
Peer-Review-Status | Ja |
Externe IDs
PubMed | 37671442 |
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ORCID | /0000-0001-7323-7816/work/163295520 |
Schlagworte
ASJC Scopus Sachgebiete
Schlagwörter
- Diphosphenes, Photoisomerization, Photoswitch, Quantum Chemical Calculations, Structure Elucidation