Show simple item record

dc.contributor.authorAlhilaly, Mohammad J.
dc.contributor.authorBootharaju, Megalamane S.
dc.contributor.authorJoshi, Chakra P
dc.contributor.authorBesong, Tabot M.D.
dc.contributor.authorEmwas, Abdul-Hamid
dc.contributor.authorMosqueda, Rosalba Juarez
dc.contributor.authorKaappa, Sami
dc.contributor.authorMalola, Sami
dc.contributor.authorAdil, Karim
dc.contributor.authorShkurenko, Aleksander
dc.contributor.authorHäkkinen, Hannu
dc.contributor.authorEddaoudi, Mohamed
dc.contributor.authorBakr, Osman M.
dc.date.accessioned2016-11-11T08:28:41Z
dc.date.available2017-10-13T21:45:07Z
dc.date.issued2016
dc.identifier.citationAlhilaly, M. J., Bootharaju, M. S., Joshi, C. P., Besong, T. M., Emwas, A.-H., Mosqueda, R. J., Kaappa, S., Malola, S., Adil, K., Shkurenko, A., Häkkinen, H., Eddaoudi, M., & Bakr, O. M. (2016). [Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster. <i>Journal of the American Chemical Society</i>, <i>138</i>(44), 14727-14732. <a href="https://doi.org/10.1021/jacs.6b09007" target="_blank">https://doi.org/10.1021/jacs.6b09007</a>
dc.identifier.otherCONVID_26274065
dc.identifier.otherTUTKAID_71496
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/51860
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 Ag67 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 [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e., Ag13, unlike the common centered Ag13 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 Ag67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag67(SPhMe2)32(PPh3)8]3+ and a reduced model [Ag67(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 Ag67 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.
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.relation.ispartofseriesJournal of the American Chemical Society
dc.subject.othersurface ligands
dc.subject.othermetal nanoparticles
dc.subject.othernanoclusters
dc.title[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201611094599
dc.contributor.laitosFysiikan laitosfi
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Physicsen
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineFysikaalinen kemiafi
dc.contributor.oppiaineNanoscience Centerfi
dc.contributor.oppiainePhysical Chemistryen
dc.contributor.oppiaineNanoscience Centeren
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2016-11-09T10:15:04Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange14727-14732
dc.relation.issn0002-7863
dc.relation.numberinseries44
dc.relation.volume138
dc.type.versionacceptedVersion
dc.rights.copyright© 2016 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.doi10.1021/jacs.6b09007
dc.type.okmA1


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record