Generation of Naphthalenediimide(II) Dianion in a Solid-State Regular π-Stacked Electron-Donor/Acceptor Coordination...

Photoinduced electron transfer (PET) for the generation of the naphthalenediimide dianion (NDI^{2 -}) in a solid-state, regular π-stacked electron donor/acceptor coordination polymer (D-A CP) is described, representing the first report of the photochemically driven synthesis of NDI^{2 -} in a solid-state D-A CP. Photoinduced one-step two-electron transfer and consecutive PET (conPET) events, as well as the formation of NDI^{2 -}, are realized under UV light (<365 nm) and visible light (>420 nm), respectively. Extensive experimental evidence and computational models confirm that the well-matched electronic energy levels between the electron donor (D) and acceptor (A), combined with the regular D-A-D-A π-stacked supramolecular interactions, facilitate these unprecedented PET events, which further endow the D-A CP with important semiconductor properties, including photocurrent generation and photo responsive behavior.