Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach.
Evgeny V TretyakovDmitry E GorbunovNina P GritsanAshok KeerthiMartin BaumgartenDieter SchollmeyerMikhail IvanovAnna SergeevaMatvey V FedinPublished in: RSC advances (2024)
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 (DPP Th -NN 2 ). 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 DPP Th -NN 2 are presented. The single-crystal X-ray diffraction analysis of DPP Th -NN 2 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 DPP Th with a small singlet-triplet splitting (Δ E ST ) of about 25 cm -1 (∼0.07 kcal mol -1 ). In turn, a strong ferromagnetic exchange interaction between the triplet state of DPP Th chromophore and nitronyl nitroxides (with J ∼ 250 cm -1 ) was predicted.