In:
Chemical Science, Royal Society of Chemistry (RSC), Vol. 13, No. 46 ( 2022), p. 13732-13740
Kurzfassung:
The metastable trilacunary heteropolyoxomolybdate [PMo 9 O 31 (py) 3 ] 3− – {PMo9}; py = pyridine) and the ditopic pyridyl bearing diarylethene (DAE) (C 25 H 16 N 2 F 6 S 2 ) self-assemble via a facile ligand replacement methodology to yield the photo-active molecular capsule [(PMo 9 O 31 ) 2 (DAE) 3 ] 6− . The spatial arrangement and conformation of the three DAE ligands are directed by the surface chemistry of the molecular metal oxide precursor with exclusive ligation of the photo-active antiparallel rotamer to the polyoxometalate (POM) while the integrity of the assembly in solution has been verified by a suite of spectroscopic techniques. Electrocyclisation of the three DAEs occurs sequentially and has been investigated using a combination of steady-state and time-resolved spectroscopies with the discovery of a photochemical cascade whereby rapid photoinduced ring closure is followed by electron transfer from the ring-closed DAE to the POM in the latent donor–acceptor system on subsequent excitation. This interpretation is also supported by computational and detailed spectroelectrochemical analysis. Ring-closing quantum yields were also determined using a custom quantum yield determination setup (QYDS), providing insight into the impact of POM coordination on these processes.
Materialart:
Online-Ressource
ISSN:
2041-6520
,
2041-6539
Sprache:
Englisch
Verlag:
Royal Society of Chemistry (RSC)
Publikationsdatum:
2022
ZDB Id:
2559110-1
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