Name:
acs2Echemmater2E5b05008.pdf
Size:
794.3Kb
Format:
PDF
Description:
Accepted Manuscript
Type
ArticleAuthors
Bootharaju, Megalamane Siddaramappa
Joshi, Chakra Prasad
Alhilaly, Mohammad Jaber

Bakr, Osman

KAUST Department
Functional Nanomaterials Lab (FuNL)KAUST Catalysis Center (KCC)
KAUST Solar Center (KSC)
Material Science and Engineering Program
Physical Science and Engineering (PSE) Division
Date
2016-04-12Online Publication Date
2016-04-12Print Publication Date
2016-05-24Permanent link to this record
http://hdl.handle.net/10754/603946
Metadata
Show full item recordAbstract
Modulating the structure-property relationship in atomically precise nanoclusters (NCs) is vital for developing novel NC materials and advancing their applications. While promising biphasic ligand-exchange (LE) strategies have been developed primarily to attain novel NCs, understanding the mechanistic aspects involved in tuning the core and the ligand-shell of NCs in such biphasic processes is challenging. Here, we design a single phase LE process that enabled us to elucidate the mechanism of how a hollow NC (e.g., [Ag44(SR)30]4-, -SR: thiolate) converts into a non-hollow NC (e.g., [Ag25(SR)18]-), and vice versa. Our study reveals that the complete LE of the hollow [Ag44(SPhF)30]4- NCs (–SPhF: 4-fluorobenzenethiolate) with incoming 2,4-dimethylbenzenethiol (HSPhMe2) induced distortions in the Ag44 structure forming the non-hollow [Ag25(SPhMe2)18]- by a disproportionation mechanism. While the reverse reaction of [Ag25(SPhMe2)18]- with HSPhF prompted an unusual dimerization of Ag25, followed by a rearrangement step that reproduces the original [Ag44(SPhF)30]4-. Remarkably, both the forward and the backward reactions proceed through similar size intermediates that seem to be governed by the boundary conditions set by the thermodynamic and electronic stability of the hollow and non-hollow metal cores. Furthermore, the resizing of NCs highlights the surprisingly long-range effect of the ligands which are felt by atoms far deep in the metal core, thus opening a new path for controlling the structural evolution of nanoparticles.Citation
Switching a Nanocluster Core from Hollow to Non-hollow 2016 Chemistry of MaterialsSponsors
Financial support for this work was provided by KAUST.Publisher
American Chemical Society (ACS)Journal
Chemistry of MaterialsAdditional Links
http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b05008ae974a485f413a2113503eed53cd6c53
10.1021/acs.chemmater.5b05008