Trityl-Aryl-Nitroxide-Based Genuinely g-Engineered Biradicals, As Studied by Dynamic Nuclear Polarization, Multifrequency ESR/ENDOR, Arbitrary Wave Generator Pulse Microwave Waveform Spectroscopy, and Quantum Chemical Calculations

Trityl-Aryl-Nitroxide-Based Genuinely g-Engineered Biradicals, As Studied by Dynamic Nuclear Polarization, Multifrequency ESR/ENDOR, Arbitrary Wave Generator Pulse Microwave Waveform Spectroscopy, and Quantum Chemical Calculations Научная публикация

Журнал

Journal of Physical Chemistry A
ISSN: 1089-5639

Вых. Данные

Год: 2019, Том: 123, Номер: 34, Страницы: 7507-7517 Страниц : 11 DOI: 10.1021/acs.jpca.9b07169

Авторы

Sato Kazunobu ¹ , Hirao Rei ¹ , Timofeev Ivan ^2,3,4 , Krumkacheva Olesya ^2,3,4 , Zaytseva Elena ^2,4 , Rogozhnikova Olga ^2,4 , Tormyshev Victor M. ^2,4 , Trukhin Dmitry ^2,4 , Bagryanskaya Elena ^2,4 , Gutmann Torsten ^5,6,7 , Klimavicius Cyvytautas ⁵ , Buntkowsky Gerd ⁵ , Sugisaki Kenji ¹ , Nakazawa Shigeaki ¹ , Matsuoka Hideto ¹ , Toyota Kazuo ¹ , Shiomi Daisuke ¹ , Takui Takeji ^1,8

Организации

1	(Данные Web of science) Osaka City Univ, Grad Sch Sci, Dept Chem & Mol Mat Sci, Sumiyoshi Ku, 3-3-138 Sugimoto, Osaka 5588585, Japan
2	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
3	(Данные Web of science) Int Tomog Ctr SB RAS, Inst Skaya 3A, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
5	(Данные Web of science) Tech Univ Darmstadt, Eduard Zintl Inst Inorgan & Phys Chem, Alarich Weiss Str 8, D-64287 Darmstadt, Germany
6	(Данные Web of science) Univ Kassel, Inst Chem, Heinrich Plett Str 40, D-34132 Kassel, Germany
7	(Данные Web of science) Univ Kassel, Ctr Interdisciplinary Nanostruct Sci & Technol, Heinrich Plett Str 40, D-34132 Kassel, Germany
8	(Данные Web of science) Osaka City Univ, Univ Adm Div, Univ Res Administrator Ctr, Res Support Dept,Sumiyoshi Ku, 3-3-138 Sugimoto, Osaka 5588585, Japan

Trityl and nitroxide radicals are connected by pi-topologically controlled aryl linkers, generating genuinely g-engineered biradicals. They serve as a typical model for biradicals in which the exchange (J) and hyperfine interactions compete with the g-difference electronic Zeeman interactions. The magnetic properties underlying the biradical spin Hamiltonian for solution, including J's, have been determined by multifrequency CW-ESR and H-1 ENDOR spectroscopy and compared with those obtained by quantum chemical calculations. The experimental J values were in good agreement with the quantum chemical calculations. The g-engineered biradicals have been tested as a prototype for AWG (Arbitrary Wave Generator)-based spin manipulation techniques, which enable GRAPE (GRAdient Pulse Engineering) microwave control of spins in molecular magnetic resonance spectroscopy for use in molecular spin quantum computers, demonstrating efficient signal enhancement of specific weakened hyperfine signals. Dynamic nuclear polarization (DNP) effects of the biradicals for 400 MHz nuclear magnetic resonance signal enhancement have been examined, giving efficiency factors of 30 for H-1 and 27.8 for C-13 nuclei. The marked DNP results show the feasibility of these biradicals for hyperpolarization.

Sato K. , Hirao R. , Timofeev I. , Krumkacheva O. , Zaytseva E. , Rogozhnikova O. , Tormyshev V.M. , Trukhin D. , Bagryanskaya E. , Gutmann T. , Klimavicius C. , Buntkowsky G. , Sugisaki K. , Nakazawa S. , Matsuoka H. , Toyota K. , Shiomi D. , Takui T.
Trityl-Aryl-Nitroxide-Based Genuinely g-Engineered Biradicals, As Studied by Dynamic Nuclear Polarization, Multifrequency ESR/ENDOR, Arbitrary Wave Generator Pulse Microwave Waveform Spectroscopy, and Quantum Chemical Calculations
Journal of Physical Chemistry A. 2019. V.123. N34. P.7507-7517. DOI: 10.1021/acs.jpca.9b07169 WOS Scopus РИНЦ

Опубликована online:	2 авг. 2019 г.
Опубликована в печати:	29 авг. 2019 г.

Web of science	WOS:000485829100019
Scopus	2-s2.0-85071679850
РИНЦ	41627140
OpenAlex	W2966619690