| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1326661 | Journal of Organometallic Chemistry | 2011 | 7 Pages |
The synthesis, structure, photophysics, and spectroscopic characterization of two novel organometallic rhodium and rhenium multichromophore photosensitizers carrying a central 2,2′-bipyridyl acceptor moiety are reported. Due to the presence of rigid phenylethynyl substituents in their 5,5′-position acting as intramolecular antenna groups, these compounds display perturbed excited state properties and a modified luminescence behaviour compared to the unsubstituted parent systems. The rhodium derivative is characterized by a weak blue–green intraligand (IL) phosphorescence occurring only at low temperatures. In the rhenium complex both a blue–green ligand-based luminescence and a red phosphorescence of metal-to-ligand charge transfer (MLCT) origin is observed at room temperature in solution. In rigid 77 K matrix the lowest-lying excited state levels approximate in energy and a structured luminescence band occurs which is ascribed to a ligand phosphorescence with admixed MLCT character.
Graphical abstractThe synthesis, structure, photophysics, and spectroscopic characterization of novel organometallic rhodium and rhenium multichromophore photosensitizers carrying a central 2,2’-bipyridyl acceptor moiety are reported. Due to the presence of phenylethynyl substituents in their 5,5’-position, these compounds display perturbed excited state properties and modified luminescence behaviour compared to the unsubstituted parent systems.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Critical assignment of the low-lying excited states in modified Re and Rh polypyridyl complexes. ► Potential new photo- and electrocatalysts for carbon dioxide reduction and hydride transfer. ► Key-components for designing conductive polymer bound catalysts and triplet emitters. ► Photophysics readily controlled by medium effects, temperature and substituents.
