Ultrafast Photoinduced Electron Transfer Between Donor (Eosin-Y) and Acceptor (Naphthoquinone) in a Supramolecular Array Based on a Coordination Cage Host

被引:0
作者
Tipping, Max B. [1 ]
Woolley, Jack M. [1 ]
Williams, James R. [1 ]
Ward, Michael D. [1 ]
机构
[1] Univ Warwick, Dept Chem, Coventry CV4 7AL, England
关键词
Supramolecular chemistry; Coordination cage; Host/guest chemistry; Photoinduced electron transfer; Crystal structure; TEMPLATING PHOTODIMERIZATION; CHARGE SEPARATION; QUANTUM YIELDS; FREE-RADICALS; STEADY-STATE; FLUORESCENCE; WATER; SURFACE; 1,4-NAPHTHOQUINONE; RECOGNITION;
D O I
10.1002/chem.202404647
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An octanuclear M8L12 coordination cage host (HPEG & sdot; M) in aqueous solution binds neutral electron-accepting guests such as naphthoquinone (NQ) in its central cavity via the hydrophobic effect, and multiple anionic photosensitisers such as Eosin-Y (EY2-) around the exterior surface due to 16+ charge on the complex cation: this is confirmed by both solution titration experiments and X-ray crystallography. In the three-component assembly HPEG & sdot; Cd/EY2-/NQ, photoexcitation of EY2- at 525 nm results in ultrafast (ca. 1 ps) photoinduced EY2--> NQ electron transfer from surface-bound EY2- to cavity-bound NQ (which have been brought into close proximity by their interactions with different sites on the host cage) to give the charge-separated pair EY & sdot;-/NQ & sdot;-, identified by transient absorption spectroscopy: back-ET results in charge recombination in approximate to 70 ps. The assembly of donor and acceptor components via orthogonal interactions using the host cage as a scaffold presents a promising route into spatial control of multiple components in supramolecular arrays for photophysical applications.
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页数:8
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