Photoinduced host-to-guest electron transfer in a self-assembled coordination cage

Abstract

Light–powered host–guest charge transfer (HGCT) is shown for a coordination cage based on electron-rich phenothiazines, containing an anthraquinone acceptor as guest. Transient absorption spectroscopy and spectroelectrochemistry data is presented. A [Pd 2 L 4 ] coordination cage, assembled from electron-rich phenothiazine-based ligands and encapsulating an electron-deficient anthraquinone-based disulfonate guest, is reported. Upon excitation at 400 nm, transient absorption spectroscopy unveils photoinduced electron transfer from the host's chromophores to the guest, as indicated by characteristic spectral features assigned to the oxidized donor and reduced acceptor. The structure of the host–guest complex was characterized by NMR spectroscopy, mass spectrometry and single-crystal X-ray analysis. Spectroelectrochemical experiments and DFT calculations both agree with the proposed light-induced charge separation. A kinetic analysis of the involved charge transfer channels reveals, besides a guest-independent LMCT path, 44% efficiency for the host–guest charge transfer (HGCT).