Near‐Infrared Luminescent Ru(II) and Os(II) Complexes

Two Ru(II) and Os(II) homoleptic complexes based on a phenanthroline-pyridylidene tridentate ligand have been designed to reach NIR emission by combining strong σ-donation, provided by the unconventional N-heterocyclic carbene (NHC) pyridylidene moiety, with the low-lying π-accepting phenanthroline scaffold. Detailed experimental and computational investigations of the photophysical properties of this novel family of cyclometallated complexes reveal emission squarely falling in the NIR domain peaking at λ<sub>em</sub> = 790 nm for the Os(II) complex, while emission is hypsochromically shifted at λ<sub>em</sub> = 747 nm for the Ru(II) homologue in deaerated CH<sub>3</sub>CN solution at room temperature. Despite the triplet metal-to-ligand charge transfer (<sup>3</sup>MLCT) nature that characterizes the excited state in both complexes, density functional theory (DFT) calculations allow to ascribe the remarkable optical shift observed in the latter to the larger spin-orbital coupling (SOC) effects exerted by the heavier metal.

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Publication Details

Journal
Chemistry - A European Journal
Published
2025-07-24
DOI
https://doi.org/10.1002/chem.202501791
Primary Topic
N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Type
article
Field-Weighted Citation Impact
0.00

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article

Near‐Infrared Luminescent Ru(II) and Os(II) Complexes

Valerio Giuso, Matteo Mauro, Cristina Cebrián, Salwa Simona Jamil et al.
Chemistry - A European Journal
N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
article

Near‐Infrared Luminescent Ru(II) and Os(II) Complexes

Valerio Giuso, Matteo Mauro, Cristina Cebrián, Salwa Simona Jamil, Philippe C. Gros, Christophe Gourlaouen
article en

Abstract

Two Ru(II) and Os(II) homoleptic complexes based on a phenanthroline-pyridylidene tridentate ligand have been designed to reach NIR emission by combining strong σ-donation, provided by the unconventional N-heterocyclic carbene (NHC) pyridylidene moiety, with the low-lying π-accepting phenanthroline scaffold. Detailed experimental and computational investigations of the photophysical properties of this novel family of cyclometallated complexes reveal emission squarely falling in the NIR domain peaking at λ<sub>em</sub> = 790 nm for the Os(II) complex, while emission is hypsochromically shifted at λ<sub>em</sub> = 747 nm for the Ru(II) homologue in deaerated CH<sub>3</sub>CN solution at room temperature. Despite the triplet metal-to-ligand charge transfer (<sup>3</sup>MLCT) nature that characterizes the excited state in both complexes, density functional theory (DFT) calculations allow to ascribe the remarkable optical shift observed in the latter to the larger spin-orbital coupling (SOC) effects exerted by the heavier metal.

Chemistry - A European JournalVol. 31(47)
Centre National de la Recherche Scientifique (FR), University of Padua (IT), Université de Strasbourg (FR), Université de Lorraine (FR)
Université de Lorraine, Agence Nationale de la Recherche, Université de Strasbourg, Centre National de la Recherche Scientifique
Openalex Percentile: Top 86%
N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
DOIOpen Access PDFOpenAlex
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Near‐Infrared Luminescent Ru(II) and Os(II) Complexes — Valerio Giuso, Matteo Mauro, et al. · Chemistry - A European Journal (2025) | TGRS Research Map | TGRS