Photoswitching of a Thermally Unswitchable Molecular Magnet Cu(hfac)(2)Li-Pr Evidenced by Steady-State and Time-Resolved Electron Paramagnetic Resonance

Photoswitching of a Thermally Unswitchable Molecular Magnet Cu(hfac)(2)Li-Pr Evidenced by Steady-State and Time-Resolved Electron Paramagnetic Resonance Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863

Output data

Year: 2014, Volume: 136, Number: 28, Pages: 10132-10138 Pages count : DOI: 10.1021/ja504774q

Authors

Barskaya Irina Yu ^1,2 , Tretyakov Evgeny V. ¹ , Sagdeev Renad Z. ^1,3 , Ovcharenko Victor I. ¹ , Bagryanskaya Elena G. ^1,2,4 , Maryunina Kseniya Yu ^1,5 , Takui Takeji ^6,7 , Sato Kazunobu ^6,7 , Fedin Matvey V. ^1,2

Affiliations

1	(Данные Web of science) Int Tomog Ctr SB RAS, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
3	(Данные Web of science) Kazan Volga Reg Fed Univ, Kazan 420008, Russia
4	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Novosibirsk 630090, Russia
5	(Данные Web of science) Hiroshima Univ, Grad Sch Sci, Dept Chem, Higashihiroshima 7398526, Japan
6	(Данные Web of science) Osaka City Univ, Grad Sch Sci, Dept Chem & Mol Mat Sci, Osaka 5588585, Japan
7	(Данные Web of science) JSPS, FIRST Quantum Informat Proc Project, Tokyo 1018430, Japan

Most photoswitchable molecular magnets exhibit thermally induced switching, as is typical of spin crossover (SCO), valence tautomerism and SCO-like phenomena. We report a rare case of a copper-nitroxide based molecular magnet Cu(hfac)(2)Li-Pr that does not exhibit quantitative SCO-like behavior in the temperature range of its chemical stability (2-350 K); however, it can be switched to a metastable thermally inaccessible spin state via visible/near-IR light at cryogenic temperatures. By means of photogeneration, unique information on this otherwise unobservable spin state has been obtained using steady-state Q-band (34 GHz) and time-resolved W-band (94 GHz) electron paramagnetic resonance (EPR) spectroscopy. In particular, we have found that the electronic structure and relaxation properties of the photoinduced state in Cu(hfac)2L(i-Pr) are very similar to those in its sister compound Cu(hfac)(2)Ln-pr that is thermally switchable and has been exhaustively characterized by many analytical methods, previously. The first observation of photoswitchable behavior in a thermally unswitchable copper-nitroxide based molecular magnet Cu(hfac)(2)Li-Pr paves the way for photoswitching applications of this and similar compounds in the remarkably broad temperature range of 2-350 K.

Barskaya I.Y. , Tretyakov E.V. , Sagdeev R.Z. , Ovcharenko V.I. , Bagryanskaya E.G. , Maryunina K.Y. , Takui T. , Sato K. , Fedin M.V.
Photoswitching of a Thermally Unswitchable Molecular Magnet Cu(hfac)(2)Li-Pr Evidenced by Steady-State and Time-Resolved Electron Paramagnetic Resonance

Journal of the American Chemical Society. 2014. V.136. N28. P.10132-10138. DOI: 10.1021/ja504774q WOS Scopus РИНЦ

Full text from publisher

Published online:	Jul 2, 2014
Published print:	Jul 16, 2014

Web of science	WOS:000339228200054
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