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Janus-type emission from a cyclometalated iron(III) complex.

Jakob Steube^1,2, Ayla Kruse^3,4, Olga S Bokareva^4,5

¹Institute of Inorganic Chemistry, Paderborn University, Paderborn, Germany.

Nature Chemistry

|February 28, 2023

Summary

Researchers developed a novel iron complex exhibiting dual emission, a first for emissive iron compounds. This breakthrough, utilizing a unique ligand design, opens doors for iron

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Area of Science:

Inorganic Chemistry
Photochemistry
Materials Science

Background:

Iron is a promising, cost-effective alternative to noble metals for photoactive applications.
Developing emissive and photoactive iron complexes is challenging due to rapid charge-transfer state deactivation.
Dual emission in iron complexes has not been previously reported.

Purpose of the Study:

To design and synthesize a novel iron complex with dual emission properties.
To investigate the origin of dual emission in iron complexes.
To explore the potential of such complexes in photoredox catalysis.

Main Methods:

Synthesis of the Fe(III) complex [Fe(ImP)2][PF6], where HImP is 1,1'-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene).
Characterization of the complex's photophysical properties, including emission spectra and lifetimes.
Ligand design incorporating N-heterocyclic carbenes and cyclometalating aryl units.

Main Results:

The synthesized iron complex exhibits Janus-type dual emission originating from ligand-to-metal charge transfer (LMCT) and metal-to-ligand charge transfer (MLCT) states.
The ligand design facilitates energetically accessible MLCT states, preventing evolution into LMCT states.
The MLCT-dominated state possesses a lifetime of 4.6 ns and exhibits strong reducing and oxidizing capabilities.

Conclusions:

A novel iron complex with unprecedented dual emission behavior has been achieved.
The unique ligand structure is key to controlling the charge-transfer states and enabling dual emission.
The emissive iron complex holds potential for future applications in photoredox catalysis.