Eight‐Electron Silver and Mixed Gold/Silver Nanoclusters Stabilized by Selenium Donor Ligands. Issue 34 (12th June 2017)

• Record Type: Journal Article
• Authors: Chang, Wan‐Ting; Lee, Po‐Yi; Liao, Jian‐Hong; Chakrahari, Kiran Kumarvarma; Kahlal, Samia; Liu, Yu‐Chiao; Chiang, Ming‐Hsi; Saillard, Jean‐Yves; Liu, C. W.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 34(2017)
• Page Start: 10178
• Page End: 10182
• Publication Date: 2017-06-12
• Subjects: galvanic replacement -- ligand exchange -- nanoclusters -- silver -- X-ray diffraction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201704800
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The first atomically and structurally precise silver‐nanoclusters stabilized by Se‐donor ligands, [Ag20 {Se2 P(O i Pr)2 }12 ] (3 ) and [Ag21 {Se2 P(OEt)2 }12 ] + (4 ), were isolated by ligand replacement reaction of [Ag20 {S2 P(O i Pr)2 }12 ] (1 ) and [Ag21 {S2 P(O i Pr)2 }12 ] + (2 ), respectively. Furthermore, doping reactions of4 with Au(PPh3 )Cl resulted in the formation of [AuAg20 {Se2 P(OEt)2 }12 ] + (5 ). Structures of3, 4, and5 were determined by single‐crystal X‐ray diffraction. The anatomy of cluster3 with an Ag20 core having C 3 symmetry is very similar to that of its dithiophosphate analogue1 . Clusters4 and5 exhibit an Ag21 and Au@Ag20 core of Oh symmetry composed of eight silver capping atoms in a cubic arrangement and encapsulating an Ag13 and Au@Ag12 centered icosahedron, respectively. Both ligand exchange and heteroatom doping result in significant changes in optical and emissive properties for chalcogen‐passivated silver nanoparticles, which have been theoretically confirmed as 8‐electron superatoms. Abstract : Silver surfer : A diselenophosphate‐protected heteronuclear [Au@Ag20 (dsep)12 ] + nanocluster was synthesized by a galvanic replacement reaction of [Ag21 (dsep)12 ] + with Au(PPh3 )Cl. The [Au@Ag12 ] 5+ core of Ih symmetry, an 8‐electron superatom, is capped on 8 of its 20 triangular faces by silver atoms arranged in a cube.