TY - JOUR

T1 - Mapping 13C hyperfine couplings and exchange interactions in short-lived charge separated states of rigid donor-bridge-acceptor dyads

AU - Zhukov, Ivan

AU - Fishman, Natalya

AU - Kiryutin, Alexey

AU - Lukzen, Nikita

AU - Steiner, Ulrich E.

AU - Vieth, Hans Martin

AU - Schäfer, Julian

AU - Lambert, Christoph

AU - Yurkovskaya, Alexandra

N1 - Funding Information: We acknowledge the Ministry of Science and Higher Education of the Russian Federation (Contract No. 075-15-2021-580) for the financial support of the work at ITC. C.L. acknowledges the Deutsche Forschungsgemeinschaft for the support of this work and the Bavarian Ministry of Education, Culture, Research, and the Fine Arts for support within the SolTech consortium. Publisher Copyright: © 2021 Author(s).

PY - 2021/12/14

Y1 - 2021/12/14

N2 - A detailed experimental study on reversible photo-induced intramolecular charge separation is presented based on nuclear magnetic resonance detection of chemically induced dynamic nuclear polarization. From variation of such polarization with the external magnetic field, the coupling constants of isotropic and anisotropic hyperfine interactions at individual 13C sites are measured in the short-lived charge separated state of dyad molecules composed of donor-bridge-acceptor parts. The objects of study were rigid donor-bridge-acceptor dyads, consisting of triarylamine as a donor, naphthalene diimide as an acceptor, and a meta-conjugated diethynylbenzene fragment as a bridge. By systematic variation of side groups in the bridging moiety, their influence on the electron withdrawing strength is traced. In combination with similar data for the 1H positions obtained previously for the same compounds [I. Zhukov et al., J. Chem. Phys. 152, 014203 (2020)], our results provide a reliable basis for the determination of the spin density distribution in the charge separated state of such dyads.

AB - A detailed experimental study on reversible photo-induced intramolecular charge separation is presented based on nuclear magnetic resonance detection of chemically induced dynamic nuclear polarization. From variation of such polarization with the external magnetic field, the coupling constants of isotropic and anisotropic hyperfine interactions at individual 13C sites are measured in the short-lived charge separated state of dyad molecules composed of donor-bridge-acceptor parts. The objects of study were rigid donor-bridge-acceptor dyads, consisting of triarylamine as a donor, naphthalene diimide as an acceptor, and a meta-conjugated diethynylbenzene fragment as a bridge. By systematic variation of side groups in the bridging moiety, their influence on the electron withdrawing strength is traced. In combination with similar data for the 1H positions obtained previously for the same compounds [I. Zhukov et al., J. Chem. Phys. 152, 014203 (2020)], our results provide a reliable basis for the determination of the spin density distribution in the charge separated state of such dyads.

UR - http://www.scopus.com/inward/record.url?scp=85121225645&partnerID=8YFLogxK

UR - https://www.elibrary.ru/item.asp?id=47543040

U2 - 10.1063/5.0073193

DO - 10.1063/5.0073193

M3 - Article

C2 - 34911300

AN - SCOPUS:85121225645

VL - 155

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 22

M1 - 224201

ER -