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dc.contributor.authorDeng, Guocheng
dc.contributor.authorMalola, Sami
dc.contributor.authorYuan, Peng
dc.contributor.authorLiu, Xianhu
dc.contributor.authorTeo, Boon K.
dc.contributor.authorHäkkinen, Hannu
dc.contributor.authorZheng, Nanfeng
dc.date.accessioned2021-03-18T11:04:57Z
dc.date.available2021-03-18T11:04:57Z
dc.date.issued2021
dc.identifier.citationDeng, G., Malola, S., Yuan, P., Liu, X., Teo, B. K., Häkkinen, H., & Zheng, N. (2021). Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties. <i>Angewandte Chemie</i>, <i>60</i>(23), 12897-12903. <a href="https://doi.org/10.1002/anie.202101141" target="_blank">https://doi.org/10.1002/anie.202101141</a>
dc.identifier.otherCONVID_51969149
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/74683
dc.description.abstractSurface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface‐capping agent displacement remain a challenge. In this work, a silver cluster, [Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ] ( Ag 14 ‐DMF , where HSPh(CF 3 ) 2 is 3,5‐bis(trifluoromethyl)benzenethiol, PPh 3 is triphenylphosphine and DMF is N,N‐Dimethylformamide), with weakly coordinated DMF ligands on the surface silver sites, was synthesized by using a mixed ligands strategy (bulky thiolates, phosphines and small solvents). The as‐prepared Ag 14 ‐DMF is a racemic mixture of chiral molecules. Owing to the unusually high surface reactivity of Ag 14 ‐DMF , the surface ligands are labile, easily dissociated or exchanged by other ligands. Based on the enhanced surface reactivity, easy modulation on the optical properties of Ag 14 by reversible “on‐off” DMF ligation was realized. The mechanism was unraveled and rationalized by density functional theory (DFT) calculations. When chiral amines were introduced to as‐prepared products, all eight surface ligands were replaced by amines and the racemic Ag 14 clusters were converted to optically pure homochiral Ag 14 clusters as evidenced by circular dichroism (CD) activity and single‐crystal X‐ray diffraction (SCXRD). This work not only provides a new insight as to how to modulate the optical properties of metal clusters, but also unveils an efficient way to obtain atomically precise homochiral clusters for specific applications.en
dc.format.mimetypeapplication/pdf
dc.languageeng
dc.language.isoeng
dc.publisherWiley
dc.relation.ispartofseriesAngewandte Chemie
dc.rightsIn Copyright
dc.subject.othersurface reactivity
dc.subject.othernanocluster
dc.subject.othernoble metal
dc.subject.otherchirality
dc.subject.othersilver
dc.titleEnhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-202103182020
dc.contributor.laitosFysiikan laitosfi
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Physicsen
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineNanoscience Centerfi
dc.contributor.oppiaineNanoscience Centeren
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.description.reviewstatuspeerReviewed
dc.format.pagerange12897-12903
dc.relation.issn1433-7851
dc.relation.numberinseries23
dc.relation.volume60
dc.type.versionacceptedVersion
dc.rights.copyright© 2021 Wiley‐VCH GmbH
dc.rights.accesslevelopenAccessfi
dc.relation.grantnumber292352
dc.relation.grantnumber319208
dc.relation.grantnumber294217
dc.subject.ysojalometallit
dc.subject.ysomolekyylit
dc.subject.ysometallit
dc.subject.ysoklusterit
dc.subject.ysorajapinnat (pinnat)
dc.subject.ysopintarakenteet
dc.subject.ysoligandit
dc.subject.ysokemia
dc.subject.ysooptiset ominaisuudet
dc.subject.ysohopea
dc.format.contentfulltext
jyx.subject.urihttp://www.yso.fi/onto/yso/p7410
jyx.subject.urihttp://www.yso.fi/onto/yso/p2984
jyx.subject.urihttp://www.yso.fi/onto/yso/p3097
jyx.subject.urihttp://www.yso.fi/onto/yso/p18755
jyx.subject.urihttp://www.yso.fi/onto/yso/p27705
jyx.subject.urihttp://www.yso.fi/onto/yso/p24448
jyx.subject.urihttp://www.yso.fi/onto/yso/p24741
jyx.subject.urihttp://www.yso.fi/onto/yso/p1801
jyx.subject.urihttp://www.yso.fi/onto/yso/p25870
jyx.subject.urihttp://www.yso.fi/onto/yso/p7409
dc.rights.urlhttp://rightsstatements.org/page/InC/1.0/?language=en
dc.relation.doi10.1002/anie.202101141
dc.relation.funderSuomen Akatemiafi
dc.relation.funderSuomen Akatemiafi
dc.relation.funderSuomen Akatemiafi
dc.relation.funderAcademy of Finlanden
dc.relation.funderAcademy of Finlanden
dc.relation.funderAcademy of Finlanden
jyx.fundingprogramAkatemiaprofessorin tehtävä, SAfi
jyx.fundingprogramAkatemiaprofessorin tutkimuskulut, SAfi
jyx.fundingprogramAkatemiaprofessorin tutkimuskulut, SAfi
jyx.fundingprogramResearch post as Academy Professor, AoFen
jyx.fundingprogramResearch costs of Academy Professor, AoFen
jyx.fundingprogramResearch costs of Academy Professor, AoFen
jyx.fundinginformationWe thank the National Key R&D Program of China (2017YFA0207302), the NNSF of China (21890752, 21731005, 21721001), and the 111 Project (B08027) for financial support. The computational work at the University of Jyväskylä was supported by the Academy of Finland (grants 292352, 294217, 319208 and H.H.’s Academy Professorship). The computations were made at the Finnish Supercomputing Center CSC.


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