Tailoring the Crystal Structure of Nanoclusters Unveiled High Photoluminescence via Ion Pairing

Handle URI:
http://hdl.handle.net/10754/627637
Title:
Tailoring the Crystal Structure of Nanoclusters Unveiled High Photoluminescence via Ion Pairing
Authors:
Bootharaju, Megalamane Siddaramappa ( 0000-0002-8276-6987 ) ; Kozlov, Sergey M.; Cao, Zhen; Shkurenko, Aleksander ( 0000-0001-7136-2277 ) ; El-Zohry, Ahmed M.; Mohammed, Omar F. ( 0000-0001-8500-1130 ) ; Eddaoudi, Mohamed ( 0000-0003-1916-9837 ) ; Bakr, Osman M. ( 0000-0002-3428-1002 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
The lack of structurally distinct nanoclusters (NCs) of identical size and composition prevented the mechanistic understanding of their structural effects on ion pairing and concomitant optical properties. To produce such highly sought NCs, we designed a new monothiolate-for-dithiolate exchange strategy that enabled the selective transformation of the structure of a NC without affecting its metal atomicity or composition. Through this method, a bimetallic [PtAg28(BDT)12(PPh3)4]4– NC (1) was successfully synthesized from [PtAg28(S-Adm)18(PPh3)4]2+ NC (2) (S-Adm, 1-adamantanethiolate; BDT, 1,3-benzenedithiolate; PPh3, triphenylphosphine). The determined X-ray crystal structure of 1 showed a PtAg12 icosahedron core and a partially exposed surface, which are distinct from a face-centered cubic PtAg12 core and a fully covered surface of 2. We reveal through mass spectrometry (MS) that 1 forms ion pairs with counterions attracted by the core charge of the cluster, which is in line with density functional simulations. The MS data for 1, 2, and other NCs suggested that such attraction is facilitated by the exposed surface of 1. The formation of ion pairs increases the photoluminescence (PL) quantum yield of 1 up to 17.6% depending on the bulkiness of the counterion. Unlike small counterions, larger ones are calculated to occupy ≤90% of the volume near the exposed cluster surface and to make the ligand shell of 1 more rigid, which is observed to increase the PL. Thus, the developed synthesis strategy for structurally different NCs of the same size and composition allows us to probe the structure–property relationship for ion pairing and concomitant PL enhancement.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Advanced Membranes and Porous Materials Research Center; Chemical Science Program; KAUST Solar Center (KSC); Materials Science and Engineering Program; Functional Materials Design, Discovery and Development (FMD3); KAUST Solar Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
Citation:
Bootharaju MS, Kozlov SM, Cao Z, Shkurenko A, El-Zohry AM, et al. (2018) Tailoring the Crystal Structure of Nanoclusters Unveiled High Photoluminescence via Ion Pairing. Chemistry of Materials 30: 2719–2725. Available: http://dx.doi.org/10.1021/acs.chemmater.8b00328.
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
26-Mar-2018
DOI:
10.1021/acs.chemmater.8b00328
Type:
Article
ISSN:
0897-4756; 1520-5002
Sponsors:
Funding for this work was provided by KAUST. For computer time, this research used the resources of the Supercomputing Laboratory at KAUST.
Additional Links:
https://pubs.acs.org/doi/10.1021/acs.chemmater.8b00328
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Functional Materials Design, Discovery and Development (FMD3); Chemical Science Program; Materials Science and Engineering Program; KAUST Catalysis Center (KCC); KAUST Solar Center (KSC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBootharaju, Megalamane Siddaramappaen
dc.contributor.authorKozlov, Sergey M.en
dc.contributor.authorCao, Zhenen
dc.contributor.authorShkurenko, Aleksanderen
dc.contributor.authorEl-Zohry, Ahmed M.en
dc.contributor.authorMohammed, Omar F.en
dc.contributor.authorEddaoudi, Mohameden
dc.contributor.authorBakr, Osman M.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2018-04-24T07:48:29Z-
dc.date.available2018-04-24T07:48:29Z-
dc.date.issued2018-03-26en
dc.identifier.citationBootharaju MS, Kozlov SM, Cao Z, Shkurenko A, El-Zohry AM, et al. (2018) Tailoring the Crystal Structure of Nanoclusters Unveiled High Photoluminescence via Ion Pairing. Chemistry of Materials 30: 2719–2725. Available: http://dx.doi.org/10.1021/acs.chemmater.8b00328.en
dc.identifier.issn0897-4756en
dc.identifier.issn1520-5002en
dc.identifier.doi10.1021/acs.chemmater.8b00328en
dc.identifier.urihttp://hdl.handle.net/10754/627637-
dc.description.abstractThe lack of structurally distinct nanoclusters (NCs) of identical size and composition prevented the mechanistic understanding of their structural effects on ion pairing and concomitant optical properties. To produce such highly sought NCs, we designed a new monothiolate-for-dithiolate exchange strategy that enabled the selective transformation of the structure of a NC without affecting its metal atomicity or composition. Through this method, a bimetallic [PtAg28(BDT)12(PPh3)4]4– NC (1) was successfully synthesized from [PtAg28(S-Adm)18(PPh3)4]2+ NC (2) (S-Adm, 1-adamantanethiolate; BDT, 1,3-benzenedithiolate; PPh3, triphenylphosphine). The determined X-ray crystal structure of 1 showed a PtAg12 icosahedron core and a partially exposed surface, which are distinct from a face-centered cubic PtAg12 core and a fully covered surface of 2. We reveal through mass spectrometry (MS) that 1 forms ion pairs with counterions attracted by the core charge of the cluster, which is in line with density functional simulations. The MS data for 1, 2, and other NCs suggested that such attraction is facilitated by the exposed surface of 1. The formation of ion pairs increases the photoluminescence (PL) quantum yield of 1 up to 17.6% depending on the bulkiness of the counterion. Unlike small counterions, larger ones are calculated to occupy ≤90% of the volume near the exposed cluster surface and to make the ligand shell of 1 more rigid, which is observed to increase the PL. Thus, the developed synthesis strategy for structurally different NCs of the same size and composition allows us to probe the structure–property relationship for ion pairing and concomitant PL enhancement.en
dc.description.sponsorshipFunding for this work was provided by KAUST. For computer time, this research used the resources of the Supercomputing Laboratory at KAUST.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acs.chemmater.8b00328en
dc.titleTailoring the Crystal Structure of Nanoclusters Unveiled High Photoluminescence via Ion Pairingen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Solar Center (KSC)en
dc.contributor.departmentMaterials Science and Engineering Programen
dc.contributor.departmentFunctional Materials Design, Discovery and Development (FMD3)en
dc.contributor.departmentKAUST Solar Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabiaen
dc.identifier.journalChemistry of Materialsen
kaust.authorBootharaju, Megalamane Siddaramappaen
kaust.authorKozlov, Sergey M.en
kaust.authorCao, Zhenen
kaust.authorShkurenko, Aleksanderen
kaust.authorEl-Zohry, Ahmed M.en
kaust.authorMohammed, Omar F.en
kaust.authorEddaoudi, Mohameden
kaust.authorBakr, Osman M.en
kaust.authorCavallo, Luigien
kaust.authorBasset, Jean-Marieen
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