The structure-properties relationship in a series of carbonyl rhenium(I) complexes based on substituted terpyridine ligands of general formula [Re(κxN-Rtpy)(CO)yL]n+ is explored by both experimental and theoretical methods. In these compounds, the terpyridine ligands adopt both bidentate (κ2N) and terdentate (κ3N) coordination modes associated with three or two carbonyls, respectively. Conversion from the κ2N to the κ3N coordination mode leads to large changes in the absorption spectra and oxidation potentials due to destabilization of the HOMO level of each complex. The absorption profiles of the κ3N complexes cover the whole visible spectra with lower maxima around 700 nm, tailing out to 800 nm, while no emission is observed with Br- as the axial ligand L. When the axial ligand is modified from the native halide to pyridine or triphenylphosphine, the lowest absorption band is blue-shifted by 60 and 90 nm, respectively. These cationic complexes are near-infrared emitters with emission maxima between 840 and 950 nm for the pyridine compounds and 780-800 nm for the triphenylphosphine compounds.

Auvray T., Del Secco B., Dubreuil A., Zaccheroni N., Hanan G.S. (2021). In-Depth Study of the Electronic Properties of NIR-Emissive κ3N Terpyridine Rhenium(I) Dicarbonyl Complexes. INORGANIC CHEMISTRY, 60(1), 70-79 [10.1021/acs.inorgchem.0c02188].

In-Depth Study of the Electronic Properties of NIR-Emissive κ3N Terpyridine Rhenium(I) Dicarbonyl Complexes

Del Secco B.
Investigation
;
Zaccheroni N.
Penultimo
Writing – Original Draft Preparation
;
2021

Abstract

The structure-properties relationship in a series of carbonyl rhenium(I) complexes based on substituted terpyridine ligands of general formula [Re(κxN-Rtpy)(CO)yL]n+ is explored by both experimental and theoretical methods. In these compounds, the terpyridine ligands adopt both bidentate (κ2N) and terdentate (κ3N) coordination modes associated with three or two carbonyls, respectively. Conversion from the κ2N to the κ3N coordination mode leads to large changes in the absorption spectra and oxidation potentials due to destabilization of the HOMO level of each complex. The absorption profiles of the κ3N complexes cover the whole visible spectra with lower maxima around 700 nm, tailing out to 800 nm, while no emission is observed with Br- as the axial ligand L. When the axial ligand is modified from the native halide to pyridine or triphenylphosphine, the lowest absorption band is blue-shifted by 60 and 90 nm, respectively. These cationic complexes are near-infrared emitters with emission maxima between 840 and 950 nm for the pyridine compounds and 780-800 nm for the triphenylphosphine compounds.
2021
Auvray T., Del Secco B., Dubreuil A., Zaccheroni N., Hanan G.S. (2021). In-Depth Study of the Electronic Properties of NIR-Emissive κ3N Terpyridine Rhenium(I) Dicarbonyl Complexes. INORGANIC CHEMISTRY, 60(1), 70-79 [10.1021/acs.inorgchem.0c02188].
Auvray T.; Del Secco B.; Dubreuil A.; Zaccheroni N.; Hanan G.S.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/872652
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