10.1021/acsnano.7b07759.s002
Papri Chakraborty
Papri
Chakraborty
Abhijit Nag
Abhijit
Nag
Ganesan Paramasivam
Ganesan
Paramasivam
Ganapati Natarajan
Ganapati
Natarajan
Thalappil Pradeep
Thalappil
Pradeep
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)
American Chemical Society
2018
CCS
van der Waals interactions
C 60 molecules link
Fullerene-Functionalized Monolayer-Protected Silver Clusters
BDT
UV
DFT
fullerene
Ag 29
cluster
ion mobility mass spectrometry
C 60
electrospray ionization mass spectrometry
2018-02-14 00:00:00
Media
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
We
report the formation of supramolecular adducts between monolayer-protected
noble metal nanoclusters and fullerenes, specifically focusing on
a well-known silver cluster, [Ag<sub>29</sub>(BDT)<sub>12</sub>]<sup>3–</sup>, where BDT is 1,3-benzenedithiol. We demonstrate
that C<sub>60</sub> 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, [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). Density functional theory (DFT)
calculations and molecular docking simulations affirm compatibility
between the cluster and C<sub>60</sub>, 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 <i>n</i> = 4 is tetrahedral, that of <i>n</i> = 8 is
a distorted cube with a cluster at the center and fullerenes at the
vertices. Another fullerene, C<sub>70</sub>, also exhibited similar
behavior. Modified clusters are expected to show interesting properties.