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Updated: Jun 9, 2025
Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Photoinduced Isomerization of [N2]2- in a Bimetallic Lutetium Complex
Mingbin Yuan1, Andrew J McNeece2, Ekaterina A Dolgopolova3
1Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
Abstract:
The first lanthanide dinitrogen photoswitch [(C5Me4H)2(THF)Lu]2(μ-η2:η2-N2), 1, is reported. 1 is a unique example of controlled isomerization between side-on and end-on coordination modes of [N2]2- in a bimetallic lutetium dinitrogen complex that results in photochromism. Near-infrared light (NIR) was used to promote this effect, as evidenced by single X-ray diffraction (XRD) connectivity and Raman data, generating the [N2]2- end-on bound isomer, [(C5Me4H)2(THF)Lu]2(μ-η1:η1-N2), 2. Although different ligands and coordinating solvents were studied to replicate and control the optical properties in 1/2, only the original configuration with C5Me4H ligands and THF as the coordinating solvent worked. Supported by the first-principles calculations, the electronic structures along with the mechanistic details of the side-on to end-on isomerization were unraveled. Preliminary reactivity studies show that 2 formed with NIR light reacts with anthracene, generating dihydroanthracene and anthracene dimers, indicating new redox reaction pathways.
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