Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach†
*a
Dmitry
Gorbunov,
b
Nina
Gritsan,
*b
Ashok
Keerthi,
c
Martin
Baumgarten,
d
Matvey
Fedin
f
Abstract
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.
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