Incorporation of One‐Dimensional Copper Idione (1D CuI) Chains Within Bimetallic Coordination Frameworks for No 2 Sensing

ABSTRACT This study introduces a bimetallic alkali‐metal coordination assembly approach to modulate the structural configurations of copper iodide (CuI) units within various Li‐A‐CuI‐INA (A + = Na + , K + , Rb + , and HINA denotes isonicotinic acid) coordination frameworks. By co‐coordinating Li + ions with other alkali metal ions (A + ) in competition for binding with INA − , the 0D discrete CuI clusters found in the monometallic compound of Li‐CuI‐INA are transformed into extended 1D chain‐like CuI modules, which are then stabilized within the resultant bimetallic Li‐A‐CuI‐INA frameworks. Supported by DFT calculations, the Li‐Rb‐CuI‐INA compound, featuring exclusively 1D stair‐like {Cu 4 I 4 } n chains, was synthesized via this bimetallic coordination assembly strategy. This compound exhibits superior chemiresistive sensing performance for NO 2 operating at room temperature (RT), rivaling the most effective sensing materials reported to date. This study highlights a promising strategy for the rational design of high‐performing chemiresistive sensing materials through the integration of DFT computational insights with crystal engineering methodologies.