Header menu link for other important links
Fullerene-Mediated Aggregation of M25(SR)18– (M = Ag, Au) Nanoclusters
Chakraborty Papri, Mondal Biswajit, Khatun Esma, Paramasivam Ganesan,
Published in ACS Publications
Volume: 124
Issue: 27
Pages: 14891 - 14900

We report fullerene (C60 and C70)-induced aggregation of atomically precise clusters, taking M25(SR)18– (M = Ag, Au and −SR is a thiolate ligand) clusters as an example. We show that dimers, trimers, tetramers, and even higher aggregates of the clusters can be created by supramolecular interaction with fullerenes. Adducts such as [{M25(SR)18}n(C60)]n− (n = 1–5), [{M25(SR)18}n(C60)n−1]n− (n = 2–5), and [{M25(SR)18}n(C60)n]n− (n = 1, 2, 3, ..., etc.) were formed, which were studied by electrospray ionization mass spectrometry. Similar adducts with C70 were also observed. Structural insights were obtained from molecular docking and density functional theory calculations. Computational studies predicted the possibility of isomerism in some of these adducts. Fullerenes linked multiple clusters, causing aggregation. Fullerenes and clusters formed host–guest complexes in such assemblies. The possibilities of coassembly between the clusters and the fullerenes were also studied in the solid state. The nature of adducts observed in the case of M25(SR)18– was completely different compared to the previously reported fullerene adducts of [Ag29(BDT)12]3– (where BDT is 1,3-benzene dithiol), in which multiple fullerenes were attached on the surface of a single cluster. Supramolecular aggregates formed in the case of M25(SR)18– were independent of the nature of the metal atoms (Ag or Au). This implied that for an appropriate geometry of the cluster weak interactions with the ligands and ion-induced dipole interactions were more important in controlling the complexation compared to the metallophilic interactions. Exploring the interaction of atomically precise clusters with fullerenes is important, as the resulting adducts can show new properties such as isomerism, chirality, charge transfer, or enhanced optical properties.

About the journal
JournalThe Journal of Physical Chemistry C
PublisherACS Publications
Open AccessNo