Noncovalent interactions, such as π–π stacking interactions, C—H...π interactions and hydrogen bonding, are important driving forces for self-assembly in the construction of functional supermolecules and materials, especially in multicomponent supramolecular systems. Herein, a novel compound based on a π-acidic naphthalene diimide derivative and a double hydroxide-bridged dinuclear Al3+ aqua ion cluster, namely bis[N,N′-bis(2-sulfonatoethyl)-1,4,5,8-naphthalene diimide] di-μ-hydroxido-bis[tetraaquaaluminium(III)] tetrahydrate, (C18H12N2O10S2)2[Al2(OH)2(H2O)8]·4H2O, was obtained using the above-mentioned common noncovalent interactions, as well as uncommon lone-pair–π interactions. Functional molecular modules were connected by these noncovalent interactions to generate obvious photochromic properties. The compound was prepared by the self-assembly of N,N′-bis(2-sulfoethyl)-1,4,5,8-naphthalene diimide and Al(NO3)3·9H2O under mixed solvothermal conditions, and was characterized in detail by single-crystal X-ray diffraction, powder X-ray diffraction and FT–IR spectroscopy. The thermal stability and photochromic properties were also investigated; furthermore, in-situ solid-state UV–Vis absorption spectroscopy and electron spin resonance (ESR) were used to clarify the photochromic mechanism.
