An Isolable, Photoswitchable N‐Heterocyclic Carbene: On‐Demand Reversible Ammonia Activation

Abstract

The first isolable, photoswitchable N‐heterocyclic carbene was synthesized and found to undergo reversible electrocyclic isomerization upon successive exposure to UV and visible radiation. The UV‐induced ring closure afforded substantial changes to the electronic structure of the dithienylethene‐based NHC, as evidenced by changes in the corresponding UV/Vis absorption and 13C NMR spectra. Likewise, molecular orbital calculations revealed diminished electron density at the carbene nucleus upon photocyclization, consistent with the enhanced electrophilicity displayed by the ring‐closed form. The photoswitchable NHC was successfully switched between its ring‐opened and ring‐closed states with high fidelity over multiple cycles. Furthermore, the ring‐closed isomer was found to undergo facile NH bond activation, allowing for the controlled capture and release of ammonia upon cycling between its isomeric states.

Document Details

Document Type
Pub Defense Publication
Publication Date
Aug 14, 2015
Source ID
10.1002/anie.201506269

Entities

People

  • Aaron J Teator
  • Christopher Bielawski
  • Jeehiun K. Lee
  • Mu Chen
  • Yuan Tian

Organizations

  • Institute for Basic Science
  • Ministry of Education
  • National Research Foundation of Korea
  • National Science Foundation
  • Office of Naval Research

Tags

Fields of Study

  • Chemistry

Readers

  • Molecular Photonics/Laser Physics
  • Organic Chemistry
  • Surface Engineering/Surface Coating Technology.

Technology Areas

  • Microelectronics
  • Space