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Lighting Up DNA in the Near-Infrared: An Os(II)-pydppn Complex with Light-Switch Behavior.

Emanuela Trovato¹, Salvatore Genovese^1,2, Maurilio Galletta³

¹Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, Università degli Studi di Messina and Centro Interuniversitario per la Conversione dell'Energia Solare (SOLARCHEM), Via F. Stagno d'Alcontres 31, 98166 Messina, Italy.

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|December 31, 2025

Summary

This summary is machine-generated.

A new osmium(II) polypyridyl complex with an extended π-system shows enhanced DNA binding and near-infrared emission. This π-expansion modulates photophysical properties, suggesting potential for luminescent probes and phototherapy.

Keywords:

DNA light-switch near-IR luminescence osmium complex

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Area of Science:

Coordination Chemistry
Photophysics
Supramolecular Chemistry

Background:

Osmium(II) polypyridyl complexes are widely studied for their photophysical properties and potential applications.
The interaction of these complexes with DNA is crucial for developing targeted therapies and diagnostic tools.
Extending the π-system of ligands can significantly alter the electronic and photophysical characteristics of metal complexes.

Purpose of the Study:

To synthesize and characterize a π-expanded osmium(II) polypyridyl complex, [Os(tpy)(pydppn)]²⁺.
To investigate the impact of the extended planar π-system on the complex's photophysical properties.
To evaluate the binding interactions of the complex with calf-thymus DNA and understand the mechanism.

Main Methods:

Synthesis and characterization of the osmium(II) complex.
Electrochemical studies (cyclic voltammetry).
UV-Vis absorption and emission spectroscopy.
DNA titration studies (UV-Vis, circular dichroism, DNA melting temperature, viscometry).
Transient absorption spectroscopy.

Main Results:

The complex [Os(tpy)(pydppn)]²⁺ exhibits enhanced electron-accepting ability compared to its analog.
It displays UV absorption and near-infrared emission (840 nm) from a long-lived ³MLCT state.
Strong evidence for intercalative DNA binding was observed, including a light-switch effect, hypochromism, and increased DNA melting temperature (ΔT_m = 8.9 °C).
DNA binding prolongs the excited-state lifetime and alters vibrational relaxation.

Conclusions:

π-system extension in osmium(II) polypyridyl complexes effectively modulates photophysical behavior and DNA affinity.
The [Os(tpy)(pydppn)]²⁺ complex demonstrates significant potential as a DNA-targeted luminescent probe.
These findings provide insights for designing novel NIR-emitting agents for bioimaging and photodynamic therapy.