Synthesis and Luminescence Properties of Two-Electron Bimetallic Cu–Ag and Cu–Au Nanoclusters via Copper Hydride Precursors

Abstract

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Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

“…Over the past decade, through the work of Liu and co-workers, the range of copperdithiocarbamate clusters has expanded greatly including examples containing hydrides [105][106][107][108] and acetylides [109][110][111][112][113] The addition of thiuram disulfide (TDS) to Cu(I) clusters leads to oxidation and the formation of [Cu(S 2 CNR 2 ) 2 ], and the kinetics and mechanism have been studied [104]. Reactions are proposed to proceed via a rapid equilibrium with adducts [Cu(S 2 CNR 2 )(TDS)], which undergo intramolecular electron transfer in a rate-determining step to afford the final Cu(II) complexes.…”

“…Over the past decade, through the work of Liu and co-workers, the range of copperdithiocarbamate clusters has expanded greatly including examples containing hydrides [105][106][107][108] and acetylides [109][110][111][112][113] ], a process that can be reversed with the loss of H 2 upon oxidation by Ce(IV). The removal of one copper and the formation of heptanuclear [Cu 7 H(µ 3 -S 2 CNR 2 ) 6 ] occurs upon further addition of [BH 4 ] − , a transformation reversed upon the addition of Cu(I) sources.…”

Reactivities of Interstitial Hydrides in a Cu11 Template: En Route to Bimetallic Clusters

“…Thestructure of 3 is shown in Figure 1f.The metal core of AuCu 11 (Figure 1g)c an be viewed as an Au-centered Cu 12 cuboctahedron with one missing vertex. In that respect, it is related to [AuCu 12 {S 2 CN n Bu 2 } 6 (CCPh) 4 ] + , [11] and [AuCu 12 -{S 2 P(O i Pr) 2 } 6 (CCPh) 4 ] + (4), [13] which display ac omplete cuboctahedral Au@Cu 12 metal core protected by six dtc/dtp ligands bridging the six square faces in a( m 2 , m 2 )m ode and four alkynyl ligands capping half of the triangular faces in a(m 3 -h 1 )fashion. Removal of one Cu + vertex in these species causes two dtp ligands switching to (m 2 , m 1 ), whereas the four others remain (m 2 , m 2 ).…”

“…TheAu-Cu and Cu-Cu distances are comparable to those found in [AuCu 12 {S 2 CN n Bu 2 } 6 (C CPh) 4 ] + , [11] and in 4. [13] TheA u@Cu 12 cuboctahedral metal core can be seen as the simplest unit of bulk fcc. TheAu@Cu 11 core in 3 can then be visualized as av acancy-defect fcc structure (Scheme 2).…”

“…[8] In these copper(I) NCs,the hydrides are clearly hydridic as they react with protons of terminal alkynes to yield medium-sized, dtp of 3.F urthermore,t he degradation of 2 and partial aggregation of 3 in solution reveal that bimetallic clusters 2 and 3 are key precursors en route to the more stable two-electron superatomic alloys,[ M@Cu 12 {S 2 P(O i Pr) 2 } 6 (C CPh) 4 ] + (M = Au, 4;A g, 5). [13] Intriguingly,t he metal core of 3,w hich can be best described as av ertex-missing Au-centered Cu 12 cuboctahedron, displays an fcc structure with av acancy defect, which is closely related to that of 4,afull fcc array. Thus,the first two-electron superatomic alloy with adefect fcc lattice is revealed in 3.…”