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Long-Lived Charge Transfer Excited States in HBC-Polypyridyl Complex Hybrids
journal contribution
posted on 2023-05-18, 19:38 authored by Elliott, ABS, Horvath, R, Sun, X-Z, Michael GardinerMichael Gardiner, Mullen, K, Lucas, NT, George, MW, Gordon, KCThe synthesis of two bipyridine-hexa-peri-hexabenzocoronene (bpy-HBC) ligands functionalized with either tBu or C12H25 and their Re(I) tricarbonyl chloride complexes are reported and their electronic properties investigated using spectroscopic and computational methods. The metal complexes show unusual properties, and we observed the formation of a long-lived excited state using time-resolved infrared spectroscopy. Depending on the solvent, this appears to be of the form Rebpy•—HBC•+ or a bpy-centered π,π* state. TD-DFT calculations support the donor–acceptor charge transfer character of these systems, in which HBC is the donor and bpy is the acceptor. The ground state optical properties are dominated by the HBC chromophore with additional distinct transitions of the complexes, one associated with MLCT 450 nm (ε > 17 000 L mol–1 cm–1) and another with a HBC/metal to bpy charge transfer, termed the MLLCT band (373 nm, ε = 66 000 L mol–1 cm–1). These assignments are also supported by resonance Raman spectroscopy.
History
Publication title
Inorganic ChemistryVolume
55Issue
10Pagination
4710-4719ISSN
0020-1669Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
United StatesRights statement
© 2016 American Chemical SocietyRepository Status
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