Electric‐Field‐Mediated Electron Tunneling of Supramolecular Naphthalimide Nanostructures for Biomimetic H2 Production

The design and synthesis of two semiconducting bis (4‐ethynyl‐bridging 1, 8‐naphthalimide) bolaamphiphiles (BENI‐COO− and BENI‐NH3+) to fabricate supramolecular metal–insulator–semiconductor (MIS) nanostructures for biomimetic hydrogen evolution under visible light irradiation is presented. A H2 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−‐NH3+‐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 6.10×108 s−1, which is five times larger than the BENI‐NH3+ nanoribbons (1.17×108 s−1). The electric field benefited significantly the electron tunneling dynamics and compensated the charge‐separated states insufficient in the BENI‐COO− nanofibers. Two charged organic semiconductors based on naphthalimide bolaamphiphiles were designed to fabricate metal–insulator–semiconductor (MIS) photosystems with opposite‐charged DuBois nickel catalysts for biomimetic H2 evolution. The photoinduced charge carriers can be efficiently separated and tunneled to the Ni collectors across salt bridges and alkyl regions to reduce protons to H2, mediated by the intermolecular electrostatic field.