Light and Temperature Control of the Spin State of Bis(p-methoxyphenyl)carbene: A Magnetically Bistable Carbene

Journal of the American Chemical Society
Paolo CostaWolfram Sander

Abstract

Bis(p-methoxyphenyl)carbene is the first carbene that at cryogenic temperatures can be isolated in both its lowest energy singlet and triplet states. At 3 K, both states coexist indefinitely under these conditions. The carbene is investigated in argon matrices by IR, UV-vis, and X-band EPR spectroscopy and in MTHF glasses by W-band EPR and Q-band ENDOR spectroscopy. UV (365 nm) irradiation of the system results in formation of predominantly the triplet carbene, whereas visible (450 nm) light shifts the photostationary equilibrium toward the singlet state. Upon annealing at higher temperatures (>10 K), the triplet is converted to the singlet; however, cooling back to 3 K does not restore the triplet. Therefore, depending on matrix temperature and irradiation conditions, matrices containing predominantly the triplet or singlet carbene can be generated. Controlling the magnetic and chemical properties of carbenes by using light of different wavelengths might be of general interest for applications such as information storage and radical-initiated polymerization processes.

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Apr 5, 2014·Angewandte Chemie·Paolo Costa, Wolfram Sander
Sep 23, 2014·Journal of the American Chemical Society·Paolo CostaWolfram Sander

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Citations

Dec 13, 2016·The Journal of Physical Chemistry. a·Jean M Standard
May 29, 2018·Chemical Communications : Chem Comm·Yan LuXiaoqing Zeng
May 29, 2018·Angewandte Chemie·Curt Wentrup
Nov 20, 2016·Chemistry : a European Journal·Sergey Z VatsadzeIgor V Alabugin
Apr 23, 2019·The Journal of Organic Chemistry·Jiahui XuJeehiun K Lee
Aug 5, 2021·Chemistry : a European Journal·Thomas LohmillerWolfram Sander

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