[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

Handle URI:
http://hdl.handle.net/10754/622496
Title:
[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster
Authors:
Alhilaly, Mohammad J.; Bootharaju, Megalamane Siddaramappa ( 0000-0002-8276-6987 ) ; Joshi, Chakra Prasad; Besong, Tabot M.D. ( 0000-0002-3572-1428 ) ; Emwas, Abdul-Hamid M.; Juarez-Mosqueda, Rosalba; Kaappa, Sami; Malola, Sami; Adil, Karim ( 0000-0002-3804-1065 ) ; Shkurenko, Aleksander ( 0000-0001-7136-2277 ) ; Hakkinen, Hannu; Eddaoudi, Mohamed ( 0000-0003-1916-9837 ) ; Bakr, Osman M. ( 0000-0002-3428-1002 )
Abstract:
Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag-67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag-67(SPhMe2)(32)(PPh3)(8)](3+). The crystal structure shows an Ag-23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag-13, core was formed through an unprecedented centered cuboctahedron, i.e., Ag-13, unlike the common centered Ag-13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag-67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag-67(SPhMe2)(32)(PPh3)(8)](3+) and a reduced model [Ag-67(SH)(32)(PH3)(8)](3+). The lowest metal-to-metal transitions in the range 500-800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag-67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.
KAUST Department:
Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Imaging and Characterization Core Lab; Functional Materials Design, Discovery and Development (FMD3)
Citation:
Alhilaly MJ, Bootharaju MS, Joshi CP, Besong TM, Emwas A-H, et al. (2016) [Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster. Journal of the American Chemical Society 138: 14727–14732. Available: http://dx.doi.org/10.1021/jacs.6b09007.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
13-Oct-2016
DOI:
10.1021/jacs.6b09007
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
The financial support for this work was provided by KAUST. The theoretical work was supported by the Academy of Finland. The computational resources were provided by CSC in Espoo, Finland.
Is Supplemented By:
Alhilaly, M. J., Bootharaju, M. S., Joshi, C. P., Besong, T. M., Emwas, A.-H., Juarez-Mosqueda, R., … Bakr, O. M. (2016). CCDC 1521591: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1n2bln; DOI:10.5517/ccdc.csd.cc1n2bln; HANDLE:http://hdl.handle.net/10754/624598
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.6b09007
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Advanced Nanofabrication, Imaging and Characterization Core Lab; Physical Sciences and Engineering (PSE) Division; Functional Materials Design, Discovery and Development (FMD3)

Full metadata record

DC FieldValue Language
dc.contributor.authorAlhilaly, Mohammad J.en
dc.contributor.authorBootharaju, Megalamane Siddaramappaen
dc.contributor.authorJoshi, Chakra Prasaden
dc.contributor.authorBesong, Tabot M.D.en
dc.contributor.authorEmwas, Abdul-Hamid M.en
dc.contributor.authorJuarez-Mosqueda, Rosalbaen
dc.contributor.authorKaappa, Samien
dc.contributor.authorMalola, Samien
dc.contributor.authorAdil, Karimen
dc.contributor.authorShkurenko, Aleksanderen
dc.contributor.authorHakkinen, Hannuen
dc.contributor.authorEddaoudi, Mohameden
dc.contributor.authorBakr, Osman M.en
dc.date.accessioned2017-01-02T09:28:34Z-
dc.date.available2017-01-02T09:28:34Z-
dc.date.issued2016-10-13en
dc.identifier.citationAlhilaly MJ, Bootharaju MS, Joshi CP, Besong TM, Emwas A-H, et al. (2016) [Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster. Journal of the American Chemical Society 138: 14727–14732. Available: http://dx.doi.org/10.1021/jacs.6b09007.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.6b09007en
dc.identifier.urihttp://hdl.handle.net/10754/622496-
dc.description.abstractEngineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag-67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag-67(SPhMe2)(32)(PPh3)(8)](3+). The crystal structure shows an Ag-23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag-13, core was formed through an unprecedented centered cuboctahedron, i.e., Ag-13, unlike the common centered Ag-13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag-67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag-67(SPhMe2)(32)(PPh3)(8)](3+) and a reduced model [Ag-67(SH)(32)(PH3)(8)](3+). The lowest metal-to-metal transitions in the range 500-800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag-67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.en
dc.description.sponsorshipThe financial support for this work was provided by KAUST. The theoretical work was supported by the Academy of Finland. The computational resources were provided by CSC in Espoo, Finland.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.6b09007en
dc.title[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanoclusteren
dc.typeArticleen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentImaging and Characterization Core Laben
dc.contributor.departmentFunctional Materials Design, Discovery and Development (FMD3)en
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionDepartments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä, Finlanden
kaust.authorAlhilaly, Mohammad J.en
kaust.authorBootharaju, Megalamane Siddaramappaen
kaust.authorJoshi, Chakra Prasaden
kaust.authorBesong, Tabot M.D.en
kaust.authorEmwas, Abdul-Hamid M.en
kaust.authorAdil, Karimen
kaust.authorShkurenko, Aleksanderen
kaust.authorEddaoudi, Mohameden
kaust.authorBakr, Osman M.en
dc.relation.isSupplementedByAlhilaly, M. J., Bootharaju, M. S., Joshi, C. P., Besong, T. M., Emwas, A.-H., Juarez-Mosqueda, R., … Bakr, O. M. (2016). CCDC 1521591: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1n2blnen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1n2blnen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624598en
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