Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

Abstract

Complementary ultrafast techniques provide clear observation of charge hopping between metals in dinuclear complexes.

Site‐Selective Real‐Time Observation of Bimolecular Electron Transfer in a Photocatalytic System Using L‐Edge X‐Ray Absorption Spectroscopy**

“…Picosecond‐ and femtosecond‐resolved X‐ray studies of a bimetallic donor‐acceptor Ru−Co complex (a prototypical photocatalytic system) have shown how ultrashort hard X‐ray spectroscopies can be efficiently used to follow both the intra‐ and intermolecular charge transfer processes at the optically silent sites of photocatalysts [36,37] . In a similar study, pump‐probe XAS, paired with all‐optical experiments, was used to investigate intramolecular electron transfer processes in a whole family of homo‐ and heterodinuclear Cu(I)/Ru(II) complexes [38] . The applicability of high‐energy resolution fluorescence detection (HERFD) [39] XAS as well as X‐ray Emission Spectroscopy (XES) to answer questions in catalysis has been further demonstrated using Fe complexes [40] .…”

Critical Role of Organic Spacers for Bright 2D Layered Perovskites Light‐Emitting Diodes

“…To connect the photo‐induced charge carrier dynamics to the electronic fine structures, we have applied time‐resolved X‐ray absorption spectroscopy (TR‐XAS) to both materials 27. The basic principle of the TR‐XAS measurement is illustrated in Figure a, where a laser pulse is used to initiate electron excitations from valence to conduction bands, creating charge carries (electron and hole pairs), followed by an X‐ray probe pulse at certain time delay to measure the electronic structure dynamics after photoexcitation (see detail discussion in Supporting Information).…”

Surface immobilized copper(i) diimine photosensitizers as molecular probes for elucidating the effects of confinement at interfaces for solar energy conversion

“…Copper(I) coordination complexes have attracted interest for integration in solar energy conversion schemes because of their broad absorption in the visible region and the relative earth abundance of copper compared to the ruthenium centre of the prototype molecular photosensitizer [Ru(bpy) 3 ] 2+ (bpy = 2,2 0bipyridine). [1][2][3][4][5][6] Recent work focused on ligand designs of Cu(I) photosensitizers has demonstrated the potential for these earth-abundant complexes to initiate light-driven H 2 catalysis in multimolecular systems. [7][8][9] Herein, we describe a fundamentally new strategy for controlling and directing photochemical processes through dimensional control of a metal oxide environment.…”