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

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 (ΔE(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.