A Sodalite-Type Silver Orthophosphate Cluster in a Globular Silver Nanocluster

Chenglong Deng; Cunfa Sun; Zhi Wang; Yunwen Tao; Yilin Chen; Jinqing Lin; Genggeng Luo; Bizhou Lin; Di Sun; Lansun Zheng

doi:10.1002/anie.202003143

A Sodalite-Type Silver Orthophosphate Cluster in a Globular Silver Nanocluster

Angew Chem Int Ed Engl. 2020 Jul 27;59(31):12659-12663. doi: 10.1002/anie.202003143. Epub 2020 May 14.

Authors

Chenglong Deng¹, Cunfa Sun¹, Zhi Wang², Yunwen Tao³, Yilin Chen¹, Jinqing Lin¹, Genggeng Luo¹, Bizhou Lin¹, Di Sun², Lansun Zheng⁴

Affiliations

¹ Key Laboratory of Environmental Friendly Function Materials, Ministry of Education, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021, P. R. China.
² Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, P. R. China.
³ Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX, 75275-0314, USA.
⁴ State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.

PMID: 32302050
DOI: 10.1002/anie.202003143

Abstract

The synthesis and structure of a giant 102-silver-atom nanocluster (NC) 1 is presented. X-ray structural analysis reveals that 1 features a multi-shelled metallic core of Ag₆ @Ag₂₄ @Ag₆₀ @Ag₁₂ . An octahedral Ag₆ core is encaged by a truncated octahedral Ag₂₄ shell. The Ag₂₄ shell is composed of a hitherto unknown sodalite-type silver orthophosphate cluster (SOC) {(Ag₃ PO₄ )₈ }, reminiscent of the Ag₃ PO₄ photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag₆ @{(Ag₃ PO₄ )₈ }S₆ ]^6- , which functions as an intricate polyhedral template with abundant surface O and S atoms guiding the formation of a rare rhombicosidodecahedral Ag₆₀ shell. An array of 6 linear Ag₂ staples further surround this Ag₆₀ shell. [Ag₆ @{(Ag₃ PO₄ )₈ }S₆ ]^6- is an unusual Ag-based templating anion to induce the assembly of a SOC within silver NC. This finding provides molecular models for bulk Ag₃ PO₄ , and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.

Keywords: anionic templates; cluster compounds; multi-shell structures; silver nanoclusters; silver orthophosphate.