Structures and magnetism of mono-palladium and mono-platinum doped Au₂₅(PET)₁₈nanoclusters

Abstract

Herein we report three important results of widespread interest, which are (1) the crystal structure of [Au24Pt(PET)18](0), (2) the crystal structure of [Au24Pd(PET)18](0) and (3) the main source of magnetism in [Au25(PET)18](0).

A molecule-like PtAu24(SC6H13)18 nanocluster as an electrocatalyst for hydrogen production

“…1a)303334. The Au 25 and Pt-doped clusters were synthesized according to the procedures reported elsewhere34 (see Supplementary Notes 1–3 for details).…”

Gold‐Doping of Double‐Crown Pd Nanoclusters

“…[1][2][3][4][5][6][7][8] Recently,a tomically precise doping of ultra small metal nanoparticles (so-called nanoclusters)h as received extensivei nterest, owing to the subtle tuning of their compositions, structures, and properties, the in-depthu nderstandingo f the doping effect, and significant efforts have been devotedt o the doping of group 11 metal nanoclusters such as Au 25 (SR) 18 , Au 38 (SR) 24 ,A g 44 (SR) 30 and Ag 25 (SR) 18 (SR:t hiolate), among which heteroatoms alwaysr eplace the substrate atoms in ao ne to one fashion. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] Although thiolated group 10 transition metal (Ni, Pd,a nd Pt) nanoclustersh ave been known for over half a century, [25][26][27][28][29] the doped double-crown structure remainsu nraveled by single crystal X-ray crystallography (SCXC) and the doping influence on the compositions, structures, and properties of Ni, Pd, or Ptnanoclustersi sy et to be known. An especially intriguing issue pertainst ot he possible chiral induction of the double-crown structure by heteroatom doping.…”

The Synthesis of Chiral Ag4Pd2(SR)8 by Nonreplaced Galvanic Reaction

“…During the past decade, atomically precise doped nanoclusters (NCs, ultrasmall nanoparticles with size less than ≈2 nm) have gained considerable attention from nanoscientists because of the synergistic or even new properties (e.g., catalytic and optical properties) of doped NCs compared to their homometallic counterparts . A general synthesis method is the synchro‐synthesis (i.e., the mixed metal precursors are concurrently reduced by reducing agent like NaBH 4 ), such as the preparation of Au 24 Pd(SR) 18 , Au 24 Pt(SR) 18 , Au 25− x Ag x (SR) 18 , Au 38− x Ag x (SR) 18 , Au 36 Pd 2 (SR) 18 , Au 36 Pt 2 (SR) 24 , Ag 24 Pd(SR) 18 , Ag 24 Pt(SR) 18 , Ag 32 Au 12 (SR) 30 , and [Au 12+ n Cu 32 (SR) 30+ n ] NCs (SR: thiolate). Due to the limitation of synchro‐synthesis in obtaining more atomically disperse alloy nanoclusters, a novel synthesis method dubbed antigalvanic reaction (AGR) was introduced by Wu in 2012 and a few atomically disperse alloy nanoclusters have been facilely obtained so far, such as Ag 2 Au 25 (SR) 18 , HgAu 24 (SR) 18 , CdAu 24 (SR) 18 , Cd 5 Au 26 (PPh 3 ) 12 (SR) 12 , and Cd 4 Au 20 (SH)(SR) 19 (Note that, AGR or pseudo‐AGR can also be employed to synthesize monometal nanoclusters, for some examples, see the syntheses of Au 28 (SR) 20 , Au 44 (SR) 32 , and Au 24 (SR) 20 .…”