Naphthalenediimide/Iodobismuthate Hybrid Heterostructures: Water Resistance and Long-Lived Charge-Separated States.

Organic-inorganic hybrid iodobismuthate perovskites have become promising semiconductive materials for their environmentally friendly and light-harvesting characteristics. However, their low-dimensional bismuth-iodide skeletons result in poor charge-separation efficiency, limiting their application in optoelectronic devices. To address this issue, the donor-acceptor (D-A) heterostructures have been introduced to the iodobismuthate hybrid materials by incorporating an electron-deficient ,'-bis(4-aminoethyl)-1,4,5,8-naphthalene diimide (NDIEA) as the electron acceptor and organic counterpart. Five naphthalenediimide/iodobismuthate hybrid heterostructures, named (HNDIEA)·BiI·3DMF (), HNDIEA·[BiI(DMF)]·2DMF (), (HNDIEA)·BiI·2HO·4MeOH (), (HNDIEA)·BiI·8HO (), and [(HNDIEA)·BiI]·4HO () (DMF = ,-dimethylformamide), were synthesized. Their crystal structures, water stabilities, charge-separated behaviors, and electrical properties have been studied through experimental and computational investigations. The results revealed that hybrids - exhibited high water resistance attributed to their tightly packed structures and robust H-bonds between solvent molecules and organic-inorganic supramolecular frameworks. Density functional theory calculations confirmed characteristic type-IIa band alignments of all the five hybrids, facilitating to the photoinduced charge separation. Moreover, the closer contact caused by the strong anion-π interactions between electron donors and acceptors in hybrid leads to the long-lived charge-separated states and improved electrical properties compared to the other hybrids.