In this work, we demonstrate the design and fabrication of a series of cylinder-like, hexazido-terminated MI-CNHC (M = Ag, Au) complexes. Moreover, we present for the first time a process-tracing and aggregation-induced emission (AIE) study of a covalent postassembly modification (PAM) process of the AuI-CNHC cylinders, highlighting the excellent versatility and complexity of functionalised poly-NHC compounds as a new type of molecular platform for novel applications.