Manipulating D-A interaction to achieve stable photoinduced organic radicals in triphenylphosphine crystals.

New strategies for the design and synthesis of stable organic radicals without additives are highly desirable. Herein, we design a series of donor-acceptor structured triarylphosphines and disclose the fast color change triggered by UV-irradiation in the crystalline state. Photoinduced organic radicals are undoubtedly verified and proved to be the reason for the color change by time-dependent and quantitative electron paramagnetic resonance analysis, X-ray crystallographic analysis, and theoretical calculations. It is revealed that the intrinsic symmetry breaking of peripheral architecture helps to form continuous molecular chains by donor-acceptor counterpart pairing. Intermolecular electron-transfer occurs among molecular chains and results in radical ion pairs upon photoirradiation.