Electrochemical triggered O-atom transfer reaction in nitrocarbonyl rhenium(I) complexes: An IR spectroelectrochemical investigation

Domínguez, Sofía Eugenia; Fagalde, Florencia

doi:10.1016/j.poly.2015.07.010

Cited by 3 publications

(1 citation statement)

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“…Previous studies on rhenium diimine complexes have indicated typical shifts from ca. −2 to −12 cm –1 for ligand-centered π,π* states, ,, while a shifts from −18 to −27 cm –1 have been reported for electrochemically reduced Re(CO) 3 Cl(bpy) and related complexes. − Therefore, in the case of R = t Bu in CH 2 Cl 2 , the shift observed for state I (−21 cm –1 ) is more consistent with an excited state in which the bpy moiety is reduced and the HBC acts as an electron donor, while state II (−7 cm –1 ) is consistent with a π,π* state with overlapping donor and acceptor, located on the bpy, HBC, or both. Similar trends are observed for most of the solvent systems, with some changes in the magnitude of the shifts.…”

Section: Resultsmentioning

confidence: 99%

Long-Lived Charge Transfer Excited States in HBC-Polypyridyl Complex Hybrids

et al. 2016

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The synthesis of two bipyridine-hexa-peri-hexabenzocoronene (bpy-HBC) ligands functionalized with either (t)Bu 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.

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