Electric‐Field‐Mediated Electron Tunneling of Supramolecular Naphthalimide Nanostructures for Biomimetic H 2 Production

The design and synthesis of two semiconducting bis (4‐ethynyl‐bridging 1, 8‐naphthalimide) bolaamphiphiles (BENI‐COO − and BENI‐NH 3 + ) to fabricate supramolecular metal–insulator–semiconductor (MIS) nanostructures for biomimetic hydrogen evolution under visible light irradiation is presented. A H 2 evolution rate of ca. 3.12 mmol g −1 ⋅h −1 and an apparent quantum efficiency (AQE) of ca. 1.63 % at 400 nm were achieved over the BENI‐COO − ‐NH 3 + ‐Ni MIS photosystem prepared by electrostatic self‐assembly of BENI‐COO − with the opposite‐charged DuBois‐Ni catalysts. The hot electrons of photoexcited BENI‐COO − nanofibers were tunneled to the molecular Ni collectors across a salt bridge and an alkyl region of 2.2–2.5 nm length at a rate of 6.10×10 8  s −1 , which is five times larger than the BENI‐NH 3 + nanoribbons (1.17×10 8  s −1 ). The electric field benefited significantly the electron tunneling dynamics and compensated the charge‐separated states insufficient in the BENI‐COO − nanofibers.