Three Semiconductive 1D Naphthalene Diimide/Iodoplumbate Perovskites with High Moisture Tolerance and Long-Lived Charge Separation States

Abstract

Low-dimensional inorganic−organic hybrid perovskites with high moisture tolerance and long-lived charge separation states have captured significant attention in the field of optoelectronic devices. To further achieve the relationship between crystal structures and stability, as well as charge separation behaviors, three one-dimensional hybrid perovskites containing electron-deficient naphthalene diimide ammonium (NDIEA) and electron-rich iodoplumbate chains, [(H 2 NDIEA)-, and [(HNDIEA) 2 Pb 2 I 6 ]•3H 2 O (3), were synthesized. Crystal structure determinations revealed various synthesis conditions leading to different stacking modes, especially the inorganic lead iodide fraction, which resulted in different water resistances and charge-separated behaviors. The comprehensive analysis found that strong intermolecular interactions (anion−π interactions and π−π interactions), and matching energy levels between protonated NDIEA and iodoplumbate chains, can facilitate the generation of long-lived charge separation states and extraordinary moisture stability, even in the water environment. In addition, the conductivity behavior of 3 was also explored in detail.

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

“…380 nm . While the long-wavelength absorption (400–800 nm) can be attributed to charge transfer (CT) from the inorganic anions to the H 2 NDIEA 2+ cations, similar absorption bands have also been observed in the reported NDI-based metal-iodide D–A hybrid complexes. ,, …”

“…Third, the accumulation modes of organic and inorganic parts are markedly different. In our previous research, the stacking modes may affect the stabilities of the NDI ammonium/metal-iodide hybrids. In hybrids 3 and 4 , organic cations assemble into the 3D HOFs with 1D channels (Figures b and b).…”

“…All chemicals were obtained from commercial sources and used without further purification. The H 2 NDIEA·2I ligand used in this work was synthesized following literature procedures . Powder X-ray diffraction (PXRD) was recorded on a Rigaku MiniFlex-II X-ray diffractometer using Cu–Kα radiation.…”

“…This configuration may be the primary factor behind the formation of long-lived charge-separated states. Until now, some NDI-based hybrid metal halides with the D–A hybrid heterostructure have been explored to achieve long-lived charge-separated states; ,− however, related research studies are still limited due to the low solubility and difficulty in crystallization of larger conjugated NDI derivatives.…”

“…This strategy employs alkylated aromatic cations instead of customary protonated organic components to build a hydrophobic environment in the hybrid perovskites. Recently, another approach, tentatively named “guest molecules assistant” strategy, has been applied by our group to construct water-stable one-dimensional (1D) hybrid lead-iodide perovskites . In this approach, the hybrid iodoplumbate obtained possesses unique attributes where all the I ions are effectively shielded by the organic cations and guest molecules through supramolecular interactions.…”