Magnetic-field-dependent delayed fluorescence from thermally activated reverse charge separation of spin-correlated charge separated states

Magnetic-field-dependent delayed fluorescence from thermally activated reverse charge separation of spin-correlated charge separated states Научная публикация

Журнал

Chemical Science
ISSN: 2041-6520

Вых. Данные

Год: 2026, Том: 17, Номер: 35, Страницы: 16842–16855 Страниц : 14 DOI: 10.1039/d6sc02081j

Авторы

Groß Tobias ¹ , Mentzel Paul ¹ , Holzapfel Marco ¹ , Schmiedel Alexander ¹ , Woodward Ben ¹ , Lukzen Nikita N. ^2,5 , Steiner Ulrich E. ³ , Lambert Christoph ^4,1

Организации

1	Institut für Organische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg 97074, Germany
2	International Tomography Center, Institutskaya 3a, Russia
3	Department of Chemistry, University of Konstanz, Universitätsstraße 10, Konstanz 78464, Germany
4	Center für Nanosystems Chemistry, Universität Würzburg, Theodor-Boveri-Weg, Würzburg 97074, Germany
5	Novosibirsk State University, 630090 Novosibirsk, Pirogova 2, Novosibirsk 630090, Russia

Thermally activated delayed fluorescence (TADF), involving reversible electron transfer between a fluorescing S1 state and a magnetically responsive charge-separated (CS) state, constitutes a sensitive probe of the spin-chemical dynamics in the CS state as well as of the local magnetic molecular environment. With (Cl)TAA-mB-PDI and SQA-pB-PDI—featuring a Cl-substituted triarylamine ((Cl)TAA) or a squaraine unit as electron donors, meta-benzene (mB) or para-benzene (pB) bridges, and a perylene diimide (PDI) unit as electron acceptor—we introduce two novel triads with sufficiently small S1–CS energy gaps to enable TADF. Their excited state properties were investigated by femtosecond and nanosecond time-resolved transient absorption spectroscopy as well as nanosecond time-resolved fluorescence spectroscopy at variable temperatures and in variable magnetic fields. The variable temperature data were used for a full kinetic and thermodynamic characterization of the reversible electron transfer in the excited state. The magnetic-field-dependent kinetic data were thoroughly analyzed using three models of increasing complexity that explicitly include the role of the S1 state: a purely classical model, a mixed quantum – classical model, and a fully quantum-dynamical model. It is shown that the magnetic-field-dependent decay of the total CS state population is well approximated by a mono-exponential function with a magnetic-field-dependent rate constant kCSS(B). Furthermore, the delayed fluorescence proves to be a reliable indicator of the spin-dependent dynamics of the CS state. Together with two structurally related triads lacking TADF, the magnetic field effects of the new systems are placed into a broader framework that categorizes such effects using three characteristic parameters: the resonance field Bres = 2J, the resonance line width (fwhm), and the relative magnetically induced kinetic range Rk of kCSS(B). We demonstrate how these characteristic parameters depend on the kinetic properties of the systems.

Groß T. , Mentzel P. , Holzapfel M. , Schmiedel A. , Woodward B. , Lukzen N.N. , Steiner U.E. , Lambert C.
Magnetic-field-dependent delayed fluorescence from thermally activated reverse charge separation of spin-correlated charge separated states
Chemical Science. 2026. V.17. N35. P.16842–16855. DOI: 10.1039/d6sc02081j WOS Scopus OpenAlex

Поступила в редакцию:	12 мар. 2026 г.
Принята к публикации:	10 июл. 2026 г.
Опубликована online:	22 июл. 2026 г.

≡ Web of science:	WOS:001826881700001
≡ Scopus:	2-s2.0-105046022900
≡ OpenAlex:	W7170091899