A Zn8 Double‐Cavity Metallacalix[8]arene as Molecular Sieve to Realize Self‐Cleaning Intramolecular Tandem Transformation of Li−S Chemistry

Abstract Toward the well‐explored lithium−sulfur (Li−S) catalytic chemistry, the slow adsorption‐migration‐conversion kinetics of lithium polysulfides on catalytic materials and Li₂S deposition‐induced passivation of active sites limit the rapid and complete conversion of sulfur. Conceptively, molecular architectures can provide atom‐precise models to understand the underlying active sites responsible for selective adsorption and conversion of LiPSs and Li₂S₂/Li₂S species. Here, an octanuclear Zn(II) (Zn₈) cluster is presented, which features a metallacalix[8]arene with double cavities up and down the Zn₈ ring. The central Zn₈ ring and the specific double cavities with organic ligands of different electronegativity and bonding environments render active sites with variable steric hindrance and interaction toward the sulfur‐borne species. An intramolecular tandem transformation mechanism is realized exclusively by Zn₈ cluster, which promotes the self‐cleaning of active sites and continuous electrochemical reaction. Notably, the external azo groups and internal Zn/O sites of Zn₈ cluster in sequence stimulate the adsorption and conversion of long chain Li₂S_x (x ≥ 4) and short chain Li₂S/Li₂S₂, contributing to remarkable rate performance and cycling stability. This work pioneers the application of metallacalix[n]arene clusters with atom‐precise structure in Li−S batteries, and the proposed mechanism advances the molecule‐level understanding of Li−S catalytic chemistry.