Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach

Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach Full article

Journal

RSC Advances
ISSN: 2046-2069

Output data

Year: 2024, Volume: 14, Number: 9, Pages: 6178-6189 Pages count : 12 DOI: 10.1039/d4ra00916a

Authors

Tretyakov Evgeny ¹ , Gorbunov Dmitry ² , Gritsan Nina ² , Keerthi Ashok ³ , Baumgarten Martin ⁴ , Schollmeyer Dieter ⁵ , Ivanov Mikhail ⁶ , Sergeeva Anna ¹ , Fedin Matvey ⁶

Affiliations

1	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Ave. 47, Moscow 119991, Russian Federation
2	V.V. Voevodsky Institute of Chemical Kinetics and Combustion, 3 Institutskaya Str., Novosibirsk 630090, Russian Federation
3	Department of Chemistry, School of Natural Sciences, The University of Manchester, Oxford Road, M13 9PL, UK
4	Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz D-55128, Germany
5	Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany
6	International Tomography Center, 3a Institutskaya Str., Novosibirsk 630090, Russian Federation

Understanding and controlling spin dynamics in organic dyes is of significant scientific and technological interest. The investigation of 2,5-dihydropyrrolo[4,3-c]pyrrolo-1,4-dione derivatives (DPPs), one of the most widely used dyes in many fields, has so far been limited to closed-shell molecules. We present a comprehensive joint experimental and computational study of DPP derivatives covalently linked to two nitronyl nitroxide radicals (DPPTh-NN2). Synthesis, single crystal X-ray diffraction study, photophysical properties, magnetic properties established using steady-state and pulse EPR, fast spin dynamics, and computational modelling using density functional theory and ab initio methods of electronic structure and spectroscopic properties of DPPTh-NN2 are presented. The single-crystal X-ray diffraction analysis of DPPTh-NN2 and computational modeling of its electronic structure suggest that effective conjugation along the backbone leads to noticeable spin-polarization transfer. Calculations using ab initio methods predict a weak exchange interaction of radical centers through a singlet ground state of DPPTh with a small singlet–triplet splitting (ΔEST) of about 25 cm−1 (∼0.07 kcal mol−1). In turn, a strong ferromagnetic exchange interaction between the triplet state of DPPTh chromophore and nitronyl nitroxides (with J ∼ 250 cm−1) was predicted.

Tretyakov E. , Gorbunov D. , Gritsan N. , Keerthi A. , Baumgarten M. , Schollmeyer D. , Ivanov M. , Sergeeva A. , Fedin M.
Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach
RSC Advances. 2024. V.14. N9. P.6178-6189. DOI: 10.1039/d4ra00916a WOS Scopus OpenAlex

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Scopus:	2-s2.0-85185843215
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