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Near-Infrared Luminescent Ru(II) and Os(II) Complexes.

Salwa Simona Jamil¹, Valerio Giuso², Christophe Gourlaouen³

¹CNRS, L2CM, Université de Lorraine, Nancy, 54000, France.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|July 25, 2025

Summary

Novel ruthenium (Ru) and osmium (Os) complexes achieve near-infrared (NIR) emission. These cyclometallated compounds, featuring N-heterocyclic carbene ligands, show distinct emission peaks due to metal-specific spin-orbital coupling effects.

Keywords:

carbene complexes near‐infrared emitters osmium complexes photophysics ruthenium complexes

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Area of Science:

Coordination Chemistry
Photophysics
Materials Science

Background:

Development of luminescent materials for near-infrared (NIR) applications is crucial.
Ruthenium(II) and Osmium(II) complexes are promising candidates for photophysical studies.
N-heterocyclic carbene (NHC) ligands offer unique electronic properties for metal complex design.

Purpose of the Study:

To design and synthesize novel Ru(II) and Os(II) homoleptic complexes with a phenanthroline-pyridylidene tridentate ligand.
To investigate the photophysical properties, particularly NIR emission, of these cyclometallated complexes.
To elucidate the factors influencing the observed emission wavelengths and excited-state characteristics.

Main Methods:

Synthesis of Ru(II) and Os(II) homoleptic complexes.
Detailed experimental photophysical characterization (emission spectroscopy).
Computational investigations using Density Functional Theory (DFT).

Main Results:

Successful design and synthesis of Ru(II) and Os(II) complexes exhibiting NIR emission.
Os(II) complex shows emission peaking at 790 nm; Ru(II) complex shows emission at 747 nm in acetonitrile.
DFT calculations indicate triplet metal-to-ligand charge transfer (³MLCT) excited states.
Larger spin-orbital coupling (SOC) in the Ru(II) complex is identified as the cause for the hypsochromic shift.

Conclusions:

The designed phenanthroline-pyridylidene ligand facilitates strong σ-donation and π-acceptance, enabling NIR emission.
The observed emission shift between Ru(II) and Os(II) complexes is primarily attributed to differences in spin-orbital coupling effects.
These findings contribute to the understanding of structure-property relationships in cyclometallated complexes for NIR applications.