A photo‐switchable hetero‐complementary quadruple H‐bonding array, which consists of an azobenzene‐derived ureidopyrimidinone (UPy) module (Azo‐UPy) and a nonphotoactive diamidonaphthyridine (DAN) derivative (Napy‐1), is constructed based on a reversible photo‐locking approach. Upon UV (390 nm)/Vis (460 nm) light irradiations, photo‐switchable quadruple H‐bonded dimerization between Azo‐UPy and Napy‐1 can be achieved with exhibiting 4.8×104‐fold differences in binding strength (ON/OFF ratios). Furthermore, smart polymeric gels with unique photo‐controlled macroscopic self‐assembly behavior can be fabricated by introducing such quadruple H‐bonding array as photo‐regulable noncovalent interfacial connections.

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