Controlled Photoinduced Generation of "Visual" Partially and Fully Charge Separated States in Viologen Analogues

Charge-separated states with a lifetime scale of seconds or longer not only favor studies using various steady-state analysis techniques but are important for light-energy conversion and other applications. Through a steric-hindrance-induced method, unprecedented photoinduced generation of a partially charge separated (PCS) state with a lifetime of days has been detected in the "visual" mode during the decay of excited states to a commonly observed fully charge separated (FCS) state for viologen analogues. One pale yellow 4,4'-bipyridine-based metalloviologen compound, with an interannular dihedral angle of 1.84° in 4,4'-bipyridine, directly decays to the purple FCS state after photoexcitation. The other pale yellow compound, with a similar coordination framework but a larger interannular dihedral angle (33.74°), changes first to a yellow PCS state and then relaxes slowly (in the dark in Ar, ca. 2 days; 70 °C in Ar, ca. 1 h) to the purple FCS state. The two-step coloration phenomenon is unprecedented for viologen compounds and their analogues and also rather rare for other photochromic species. EPR and Raman data reveal that photoinduced charge separation first generates univalent zinc and radicals and then the received electron in Zn(I) slowly distributes further to 4,4'-bipyridine. Reduction of π-conjugation and a direct to indirect change in band gap account for the prolongation of the relaxation process and the capture of the PCS state. These findings help to understand and control decay processes of excited states and provide a potential design strategy for multicolor photochromism, light-energy conversion with high efficiency, or other applications.