Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2024 May 15;146(19):13210-13225.
doi: 10.1021/jacs.4c01138. Epub 2024 May 6.

Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis

Martin Rölz  1 , Burkhard Butschke  2 , Bernhard Breit  1
Affiliations

Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis

Martin Rölz et al. J Am Chem Soc. .

Abstract

A new class of photoswitchable NHC ligands, named azImBA, has been developed by integrating azobenzene into a previously unreported imidazobenzoxazol-1-ylidene framework. These rigid photochromic carbenes enable precise control over confinement around a metal's coordination sphere. As a model system, gold(I) complexes of these NHCs exhibit efficient bidirectional E-Z isomerization under visible light, offering a versatile platform for reversibly photomodulating the reactivity of organogold species. Comprehensive kinetic studies of the protodeauration reaction reveal rate differences of up to 2 orders of magnitude between the E and Z isomers of the NHCs, resulting in a quasi-complete visible-light-gated ON/OFF switchable system. Such a high level of photomodulation efficiency is unprecedented for gold complexes, challenging the current state-of-the-art in photoswitchable organometallics. Thorough investigations into the ligand properties paired with structure-reactivity correlations underscored the unique ligand's steric features as a key factor for reactivity. This effective photocontrol strategy was further validated in gold(I) catalysis, enabling in situ photoswitching of catalytic activity in the intramolecular hydroalkoxylation and -amination of alkynes. Given the significance of these findings and its potential as a widely applicable, easily customizable photoswitchable ancillary ligand platform, azImBA is poised to stimulate the development of adaptive, multifunctional metal complexes.

PubMed Disclaimer

Similar articles

See all similar articles

Cited by

LinkOut - more resources