Bi₃₈ Oxocarboxylate Cages are Keplerates – Synthesis and Structural Characterization of Two Bi₃₈ Oxocarboxylate Cages

Abstract

The reaction of 3,5-dinitrobenzenecarboxylic acid with triphenylbismuth in a 1:1 stoichiometric ratio in toluene under reflux afforded two new Bi 38 oxocarboxylate cages [Bi 38 (μ 3 -O) 22 (μ 4 -O) 22 (μ 6 -O){3,5-(NO 2 ) 2 C 6 H 3 OO} 20 (OH) 4 (DMSO) 16 ]· 4DMSO·11H 2 O (1, DMSO = dimethyl sulfoxide) and [Bi 38 (μ 3 -O) 22 (μ 4 -O) 22 (μ 6 -O){3,5-(NO 2 ) 2 C 6 H 3 COO} 20 (CH 3 COO) 2 (OH) 2 -(DMF) 10 ]·15DMF·20H 2 O (2, DMF = N,N-dimethylformamide), which were obtained under different crystallization conditions. Compounds 1 and 2 are built from the coordination action of carboxylato, hydroxido, and oxido ligands and [a]Various types of bismuth compounds such as carboxylates, alkoxides, and siloxides are sensitive to hydrolysis, which results in the formation of oxo clusters. [12] Adven-Scheme 2. Synthesis of 1 and 2.

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

“…Among the nuclearities observed for that ligand alone are [ Oxidoclusters supported by alkoxides, other carboxylates and hexafluoroacetylacetonate have also been reported. 7,30,31,[33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] They contain a core composed of Bi(III) and oxygen atoms that has an overall positive charge. These cores are then surrounded by negatively charged carboxylate ligands to form an overall neutral compound.…”

“…The products of the hydrolysis of bismuth nitrate and perchlorate have been studied crystallographically and show the formation of discrete oxido cluster species. ,,− Complexes with salicylate (H 2 sal = HO-2-C 6 H 4 CO 2 H) were particularly of interest owing to the known biological activity of bismuth subsalicylate. Among the nuclearities observed for that ligand alone are [Bi 4 (μ 3 -O) 2 (Hsal) 8 ]·2Solv (Solv = MeCN or MeNO 2 ), [Bi 9 O 7 (Hsal) 13 (Me 2 CO) 1.5 ]·(Me 2 CO) 1.5 , [Bi 22 O 24 (Hsal) 14 ], , [Bi 38 O 45 (Hsal) 22 (OH) 2 (DMSO) 16.5 ]·DMSO-·H 2 O, , and [Bi 38 O 44 (Hsal) 26 (Me 2 CO) 16 (H 2 O) 2 ]·(Me 2 CO) 4 . ,, Oxido-clusters supported by alkoxides, other carboxylates, and hexafluoroacetylacetonate have also been reported. ,,,− They contain a core composed of Bi­(III) and oxygen atoms that has an overall positive charge. These cores are then surrounded by negatively charged carboxylate ligands to form an overall neutral compound.…”

Platonic and Archimedean solids in discrete metal-containing clusters

“…Similar Keplerate Bi 38 clusters can also be obtained with other carboxylic acid ligands. 206–211 In 2022, Zhang et al prepared a series of Ti x -coated Bi 38 heterometallic clusters, Bi 38 @Ti x ( x = 14, 16, 18 and 20). The sensitized outer shell (Ti x ) of Bi 38 @Ti x clusters can regulate and influence the photocurrent response and CO 2 cycloaddition reaction.…”

“…Compared with transition metal clusters, the main group metal (Al, 61,81,82,591,592 Ga, 62,81,82,593 In, 63 Sn, 64,594 Pb, 65 Sb, 595,596 Bi, 66,204–212 etc. ) clusters that meet the theme of this review are relatively scarce.…”

Real-Time Observation of “Soft” Magic-Size Clusters during Hydrolysis of the Model Metallodrug Bismuth Disalicylate

“…The clusters have only 2-fold symmetry, with 57 fractional coordinates for the Bi sites alone. We hence took inspiration from the observation that the {Bi 38 O 44 } core is a distorted keplerate, 23 made up of shells of a nested octahedron, cube, and truncated octahedron. Assuming that only the amplitude of the distortion is reduced in the solution phase, we parametrized it using the shifts shown in Figure 3c.…”