%0 Online Multimedia
%A Chakraborty, Papri
%A Nag, Abhijit
%A Paramasivam, Ganesan
%A Natarajan, Ganapati
%A Pradeep, Thalappil
%D 2018
%T Fullerene-Functionalized
Monolayer-Protected Silver
Clusters: [Ag29(BDT)12(C60)n]3– (n = 1–9)
%U https://acs.figshare.com/articles/media/Fullerene-Functionalized_Monolayer-Protected_Silver_Clusters_Ag_sub_29_sub_BDT_sub_12_sub_C_sub_60_sub_sub_i_n_i_sub_sup_3_sup_i_n_i_1_9_/5899138
%R 10.1021/acsnano.7b07759.s002
%2 https://acs.figshare.com/ndownloader/files/10508413
%K CCS
%K van der Waals interactions
%K C 60 molecules link
%K Fullerene-Functionalized Monolayer-Protected Silver Clusters
%K BDT
%K UV
%K DFT
%K fullerene
%K Ag 29
%K cluster
%K ion mobility mass spectrometry
%K C 60
%K electrospray ionization mass spectrometry
%X We
report the formation of supramolecular adducts between monolayer-protected
noble metal nanoclusters and fullerenes, specifically focusing on
a well-known silver cluster, [Ag29(BDT)12]3–, where BDT is 1,3-benzenedithiol. We demonstrate
that C60 molecules link with the cluster at specific locations
and protect the fragile cluster core, enhancing the stability of the
cluster. A combination of studies including UV–vis, high-resolution
electrospray ionization mass spectrometry, collision-induced dissociation,
and nuclear magnetic resonance spectroscopy revealed structural details
of the fullerene-functionalized clusters, [Ag29(BDT)12(C60)n]3– (n = 1–9). Density functional theory (DFT)
calculations and molecular docking simulations affirm compatibility
between the cluster and C60, resulting in its attachment
at specific positions on the surface of the cluster, stabilized mainly
by π–π and van der Waals interactions. The structures
have also been confirmed from ion mobility mass spectrometry by comparing
the experimental collision cross sections (CCSs) with the theoretical
CCSs of the DFT-optimized structures. The gradual evolution of the
structures with an increase in the number of fullerene attachments
to the cluster has been investigated. Whereas the structure for n = 4 is tetrahedral, that of n = 8 is
a distorted cube with a cluster at the center and fullerenes at the
vertices. Another fullerene, C70, also exhibited similar
behavior. Modified clusters are expected to show interesting properties.
%I ACS Publications