Tri-metallic deltahedral Zintl ions: experimental and theoretical studies of the novel dimer [(Sn6Ge2Bi)2]4−

Abstract

We report the synthesis, characterization, and computational rationalization of the first trimetallic deltahedral Zintl ions. The novel nine-atom clusters were structurally characterized as dimers of [(Sn(6)Ge(2)Bi)(2)](4-) with Ge-Ge intercluster bonds. They are synthesized either by reacting bimetallic clusters (Sn(9-x)Ge(x))(4-) with BiPh(3) or by direct extraction from precursors with nominal composition "K(4)Ge(4)Sn(4)Bi".

(Ge4Bi14)4−: A Case of “Element Segregation” on the Molecular Level

“…[11] Binary (E 13 x Bi y ) qÀ and (E 14 x Bi y ) qÀ (E 13 = Ga, In, Tl;E 14 = Ge,Sn, Pb) polyanions not featuring endohedral atoms have also proved as ynthetic challenge.E xamples have been limited to the 4-atom clusters,( EE'Bi 2 ) 2À (E = Ga, In, E' = Bi;E= E' = Sn, Pb), [12] the 9-atom clusters,(E 4 E' 3 Bi 2 ) qÀ (E = In, E' = Bi, q = 3; E= E' = Sn, Pb, q = 2), [12b,c,13] and the (binary or ternary) dimers of 9-atom clusters,( E 2 E' 6 Bi) 2 4À (E = E' = Ge;E = Ge,E ' = Sn). [14] As eries of (Sn 9ÀmÀn Ge m Bi n ) (4Àn)À anions were also calculated and rationalized by means of mass spectrometry. [15] In all of these examples the clusters adopt adeltahedral geometry typical of Group 14 Zintl anions,E 14…”

Subtle Impact of Atomic Ratio, Charge and Lewis Basicity on Structure Selection and Stability: The Zintl Anion [(La@In2Bi11)(μ‐Bi)2(La@In2Bi11)]6−

“…Bridged polyanions have been known mainly from the chemistry of [Ge 9 ] 4− ions, which were aggregated into GeGe bonded dimers, oligomers, and polymers by oxidative coupling 10. Another route into a GeGe bonded, ternary Tt/Tt′/Pn cluster dimer, [(Sn 6 Ge 2 Bi) 2 ] 4− , by extraction of a quaternary precursor with the nominal composition “K 4 Sn 4 Ge 4 Bi” by en and subsequent layering by toluene/[2.2.2]crypt, was reported very recently 11. Here, the observation of cluster bridging was indicative for the usefulness of such phases for the formation of nanostructured materials, such as has been realized in the synthesis of mesoporous Ge from K 4 Ge 9 3c–e…”

“…[10] Another route into a Ge À Ge bonded, ternary Tt/Tt'/Pn cluster dimer, [(Sn 6 Ge 2 Bi) 2 ] 4À , by extraction of a quaternary precursor with the nominal composition "K 4 Sn 4 Ge 4 Bi" by en and subsequent layering by toluene/A C H T U N G -T R E N N U N G [2.2.2]crypt, was reported very recently. [11] Here, the observation of cluster bridging was indicative for the usefulness of such phases for the formation of nanostructured materials, such as has been realized in the synthesis of mesoporous Ge from K 4 Ge 9 . [3c-e] Instead of a co-crystallization of diverse cage types, only the cage with 13 vertices was thus obtained, according to the assumptions quoted in the introduction.…”

(Ge4Bi14)4−: Ein Fall von “Element‐Entmischung” auf molekularer Skala

“…(E = E' = Ge;E = Ge,E ' = Sn). [14] Zusätzlich wurden die Anionen der Serie (Sn 9ÀmÀn Ge m Bi n ) (4Àn)À berechnet und mittels Massenspektrometrie nachgewiesen. [15] [17] wenn auch in heteroatomarer Form.…”

“…Bisher kennt man nur die 4-atomigen Cluster (EE'Bi 2 ) 2À (E = Ga, In, E' = Bi;E= E' = Sn, Pb), [12] die 9-atomigen Cluster (E 4 E' 3 Bi 2 ) qÀ (E = In, E' = Bi, q = 3; E= E' = Sn, Pb, q = 2) [12b,c,13] und (binäre oder ternäre) Dimere 9-atomiger Cluster,(E 2 E' 6 Bi) 2 4À (E = E' = Ge;E = Ge,E ' = Sn). [14] Zusätzlich wurden die Anionen der Serie (Sn 9ÀmÀn Ge m Bi n ) (4Àn)À berechnet und mittels Massenspektrometrie nachgewiesen. [15] In all diesen Fällen liegen Cluster mit deltaedrischem Bau vor,w ie es für die Zintl-Anionen der Gruppe 14, E 14 x qÀ ,t ypisch ist.…”