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Surface modifications of eight-electron palladium silver superatomic alloys

Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron...

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Autores principales: Barik, Subrat Kumar, Chen, Chih-Yuan, Chiu, Tzu-Hao, Ni, Yu-Rong, Gam, Franck, Chantrenne, Isaac, Kahlal, Samia, Saillard, Jean-Yves, Liu, C. W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814913/
https://www.ncbi.nlm.nih.gov/pubmed/36697889
http://dx.doi.org/10.1038/s42004-022-00769-2
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author Barik, Subrat Kumar
Chen, Chih-Yuan
Chiu, Tzu-Hao
Ni, Yu-Rong
Gam, Franck
Chantrenne, Isaac
Kahlal, Samia
Saillard, Jean-Yves
Liu, C. W.
author_facet Barik, Subrat Kumar
Chen, Chih-Yuan
Chiu, Tzu-Hao
Ni, Yu-Rong
Gam, Franck
Chantrenne, Isaac
Kahlal, Samia
Saillard, Jean-Yves
Liu, C. W.
author_sort Barik, Subrat Kumar
collection PubMed
description Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic palladium silver nanoalloys [PdAg(20){S(2)PR(2)}(12)], 2a–c (where R = O(i)Pr, a; O(i)Bu, b; Ph, c) via ligand exchange and/or co-reduction methods. The ligand exchange reaction on [PdAg(20){S(2)P(O(n)Pr)(2)}(12)], 1, with [NH(4){Se(2)PR(2)}(12)] (where R = O(i)Pr, or O(n)Pr) leads to the formation of [PdAg(20){Se(2)P(O(i)Pr)(2)}(12)] (3) and [PdAg(20){Se(2)P(O(n)Pr)(2)}(12)] (4), respectively. Solid state structures of 2a, 2b, 3 and 4 unravel different PdAg(20) metal frameworks from their parent cluster, originating from the different distributions of the eight-capping silver(I) atoms around a Pd@Ag(12) centered icosahedron with C(2,) D(3,) T(h) and T(h) symmetries, respectively. Surprisingly ambient temperature crystallization of the reaction product 3 obtained by the ligand exchange reaction on 1 has resulted in the co-crystallization of two isomers in the unit cell with overall T (3a) and C(3) (3b) symmetries, respectively. To our knowledge, this is the first ever characterized isomeric pair among the selenolate-protected NCs. Density functional theory (DFT) studies further rationalize the preferred geometrical isomerism of the PdAg(20) core.
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spelling pubmed-98149132023-01-10 Surface modifications of eight-electron palladium silver superatomic alloys Barik, Subrat Kumar Chen, Chih-Yuan Chiu, Tzu-Hao Ni, Yu-Rong Gam, Franck Chantrenne, Isaac Kahlal, Samia Saillard, Jean-Yves Liu, C. W. Commun Chem Article Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic palladium silver nanoalloys [PdAg(20){S(2)PR(2)}(12)], 2a–c (where R = O(i)Pr, a; O(i)Bu, b; Ph, c) via ligand exchange and/or co-reduction methods. The ligand exchange reaction on [PdAg(20){S(2)P(O(n)Pr)(2)}(12)], 1, with [NH(4){Se(2)PR(2)}(12)] (where R = O(i)Pr, or O(n)Pr) leads to the formation of [PdAg(20){Se(2)P(O(i)Pr)(2)}(12)] (3) and [PdAg(20){Se(2)P(O(n)Pr)(2)}(12)] (4), respectively. Solid state structures of 2a, 2b, 3 and 4 unravel different PdAg(20) metal frameworks from their parent cluster, originating from the different distributions of the eight-capping silver(I) atoms around a Pd@Ag(12) centered icosahedron with C(2,) D(3,) T(h) and T(h) symmetries, respectively. Surprisingly ambient temperature crystallization of the reaction product 3 obtained by the ligand exchange reaction on 1 has resulted in the co-crystallization of two isomers in the unit cell with overall T (3a) and C(3) (3b) symmetries, respectively. To our knowledge, this is the first ever characterized isomeric pair among the selenolate-protected NCs. Density functional theory (DFT) studies further rationalize the preferred geometrical isomerism of the PdAg(20) core. Nature Publishing Group UK 2022-11-19 /pmc/articles/PMC9814913/ /pubmed/36697889 http://dx.doi.org/10.1038/s42004-022-00769-2 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Barik, Subrat Kumar
Chen, Chih-Yuan
Chiu, Tzu-Hao
Ni, Yu-Rong
Gam, Franck
Chantrenne, Isaac
Kahlal, Samia
Saillard, Jean-Yves
Liu, C. W.
Surface modifications of eight-electron palladium silver superatomic alloys
title Surface modifications of eight-electron palladium silver superatomic alloys
title_full Surface modifications of eight-electron palladium silver superatomic alloys
title_fullStr Surface modifications of eight-electron palladium silver superatomic alloys
title_full_unstemmed Surface modifications of eight-electron palladium silver superatomic alloys
title_short Surface modifications of eight-electron palladium silver superatomic alloys
title_sort surface modifications of eight-electron palladium silver superatomic alloys
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814913/
https://www.ncbi.nlm.nih.gov/pubmed/36697889
http://dx.doi.org/10.1038/s42004-022-00769-2
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