Self‐Assembly and Humidity‐Adaptive Memristive Behavior of Benzophosphole Nanohoops

Controlling the condensed‐state properties of π‐conjugated macrocycles via molecular structure remains a fundamental challenge in supramolecular chemistry. Here, we report benzophosphole‐embedded nanohoops as a heteroatom‐doped platform where spatial configuration ( exo vs. endo ) directly governs molecular conformation, self‐assembly, and electronic function. The endo ‐nanohoop adopts a unique outward‐facing conformer that assembles into discrete tetrameric cage‐like assemblies stabilized by cooperative P═O···H 2 O interactions, which further evolve into hierarchical hollow nanobowl architectures exhibiting aggregation‐induced emission enhancement (AIEE). This differentiation generates distinct hydration microenvironments that correlate with divergent memristive behaviors. The exo ‐analogues exhibit highly uniform volatile threshold switching arising from transient ion migration dynamics, enabling physical reservoir computing. In contrast, the endo ‐framework possesses a distinct hydration microenvironment and exhibits robust analog non‐volatile memory behavior. Available evidence suggests a possible mechanism in which water acts as structural nodes that bridge Ag clusters and coordinate ion transport with filament stability, thereby enabling non‐volatile memristive behavior. Leveraging the humidity‐dependent switching characteristics of the exo system, we further demonstrate a humidity‑sensitive resistive switching capable of real‐time and noise‐resistant respiratory monitoring. These findings establish a direct correlation between molecular structure, water confinement, and adaptive electronic functionality, providing a supramolecular strategy for designing intelligent organic memristive materials and sensing‐memory integrated hardware.