2021
DOI: 10.1021/jacs.1c02653
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Insights into Formation and Relationship of Multimetallic Clusters: On the Way toward Bi-Rich Nanostructures

Abstract: Bismuth-rich polyanions show a unique potential in constructing nanostructured bismuth-based materials, but they are still poorly investigated. We use a ternary precursor of the nominal composition "K 5 Ga 2 Bi 4 " for the formation of [K(crypt-222)] + salts of novel Bi-rich polyanions [Bi@Ga 8 (Bi 2 ) 6 ] q− (q = 3, 5; in 1), (Ga 2 Bi 16 ) 4− (in 2), and [{Ru(cod)} 4 Bi 18 ] 4− (in 3). Their bismuth contents exceed that of the largest homoatomic polyanion, Bi 11 3− . The numbers of bismuth atoms in the anions… Show more

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Cited by 26 publications
(47 citation statements)
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“…Cl, for instance. [19,31,24] We were interested to get insight into the bonding situations of the anions in compounds 1 and 2. For this, density functional theory (DFT) calculations [32] were carried out with the TPSSh functional [33] and def2-TZVP basis sets.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Cl, for instance. [19,31,24] We were interested to get insight into the bonding situations of the anions in compounds 1 and 2. For this, density functional theory (DFT) calculations [32] were carried out with the TPSSh functional [33] and def2-TZVP basis sets.…”
Section: Resultsmentioning
confidence: 99%
“…Consequently, only few clusters have so far been reported, in which Ga or In and Bi coexist, such as [Sm@Ga 3− x H 3−2 x Bi 10+ x ] 3− ( x =0, 1) [28] or {[La@In 2 Bi 11 ] 2 Bi 2 } 6− , [29] while there are several examples for the TlBi‐elemental combination. These were reported as salts of binary anions, like [K(crypt‐222)] 2 ‐(TlBi 3 ), [K(crypt‐222)] 3 (Tl 4 Bi 5 ), and [K(crypt‐222)] 3 ‐(Tl 4 Bi 3 ), [30] or as salts of ternary clusters like [{Ru(cod)} 4 Bi 18 ] 4− , [U@Bi 12 ] 3− , [Th@Bi 12 ] 4− , [{Ru(cod)}Tl 2 Bi 6 ] 2− , [U@Tl 2 Bi 11 ] 3− , or [Th@Tl 2 Bi 11 ] 3− , which were obtained from reactions of (TlBi 3 ) 2− with d‐block or f‐block metal compounds [Ru(cod){H 2 CC(Me)CH 2 } 2 ], [UCp # 3 ] or [ThCp # 3 ]Cl, for instance [19, 31, 24] …”
Section: Resultsmentioning
confidence: 99%
“…The anion in compound 3 exhibits a yet unknown molecular structure, which is related, yet not identical to those reported for (Ge 4 Bi 14 ) 4À or (Ga 2 Bi 16 ) 4À . [4,6] The molecular architecture and the bonding situation of the anion in 3 will be discussed in comparison with the corresponding properties of the structurally related anion in 4 below.…”
Section: Methodsmentioning
confidence: 99%
“…Consequently, a series of intermetalloid or heterometallic clusters were reported, such as [U@Pb 7 Bi 7 ] 3− , [Th@Bi 12 ] 4− , [Bi@Ga 8 (Bi 2 ) 6 ] q− (q = 3, 5), and [(Bi 6 )Zn 3 (TlBi 5 )] 4− . [22][23][24][25] On the other hand, reactions with softer Lewis acids like the Au(I) cation, (Tt 2 Pn 2 ) 2− anions can also stay intact in the resulting complexes [Au{η 2 -(Tt 2 Pn 2 )} 2 ] 3− (Tt/Pn = Sn/Sb, Sn/Bi, and Pb/Bi). 1,26,27 To understand the limits of such decisions pro-or contradeconstruction of the tetrahedral units, it is essential to further explore these heavy atom anions in the context of atom exchange, fragmentation, and reorganization reactions.…”
Section: (Ttmentioning
confidence: 99%
“…In contrast, the heavier analogs of (Ge 2 Pn 2 ) 2− , such as (Tt 2 Pn 2 ) 2− (Tt = Sn/Pb, Pn = Sb/Bi) and (TrBi 3 ) 2− (Tr = Ga, In, Tl), tend to undergo fragmentation and reorganization upon interaction with Lewis‐acidic d‐/f‐block compounds. Consequently, a series of intermetalloid or heterometallic clusters were reported, such as [U@Pb 7 Bi 7 ] 3− , [Th@Bi 12 ] 4− , [Bi@Ga 8 (Bi 2 ) 6 ] q − ( q = 3, 5), and [(Bi 6 )Zn 3 (TlBi 5 )] 4− 22–25 . On the other hand, reactions with softer Lewis acids like the Au(I) cation, (Tt 2 Pn 2 ) 2− anions can also stay intact in the resulting complexes [Au{η 2 ‐(Tt 2 Pn 2 )} 2 ] 3− (Tt/Pn = Sn/Sb, Sn/Bi, and Pb/Bi) 1,26,27 …”
Section: Introductionmentioning
confidence: 99%