Generation of Naphthalenediimide(II) Dianion in a Solid‐State Regular π‐Stacked Electron‐Donor/Acceptor Coordination Polymer Enabled by Photochemistry

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