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ABSTRACT Supramolecular chemistry leverages non‐covalent interactions to form well‐defined structures that significantly influence electronic properties, pursuing nanoscaled electronic devices. Fullerenes, particularly C 60 , are pivotal in constructing carbon nanomaterials due to their spherical shape, which complements curved π‐conjugated hosts like cycloparaphenylenes ( n CPPs). This study explores the host–guest aggregation between the all‐metal icosahedral W@Au 12 cluster and n CPPs, comparing it to the prototypical C 60 ⊄10CPP complex. The W@Au 12 cluster, with a diameter comparable to C 60 , exhibits favorable incorporation into the 8CPP cavity. Energy decomposition analysis (EDA) reveals contrasting interaction characteristics, while C 60 ⊂10CPP stabilization is dominated by London dispersion, W@Au 12 ⊂ n CPP complexes show increased electrostatic and orbital contributions. Charge transfer analyses indicate a n CPP to W@Au 12 electron donation, with stronger coupling in partially incorporated complexes. UV–vis absorption spectra exhibit red‐shifted peaks upon cluster inclusion, with natural transition orbital analysis confirming photoinduced electron transfer from W@Au 12 to the n CPP host, contrasting the fullerene system. These findings highlight the unique supramolecular behavior of all‐metal clusters within organic hosts, offering insights into novel host–guest assemblies and guiding future experimental synthesis of cluster‐based functional materials.
Guajardo‐Maturana et al. (Fri,) studied this question.