Impact of the Exchange of the Coordinating Solvent Shell in [Bi₃₈O₄₅(OMc)₂₄(dmso)₉] by Alcohols: Crystal Structure, Gas Phase Stability, and Thermoanalysis

Abstract

Recrystallization of the bismuth oxido cluster [Bi38O45(OMc)24(dmso)9]·2dmso·7H2O (A) (OMc = O2C4H5) from alcohols such as EtOH and iPrOH gave single crystals of the bismuth oxido clusters [Bi38O45(OMc)24(ROH)x(H2O)y] [R = Et, x = 13, y = 0 (1); R = iPr, x = 10, y = 2 (2)]. Both compounds crystallize in the triclinic space group P1 and exhibit minor deviations in their cell parameters [1: a = 17.0156(5) Å, b = 19.0048(5) Å, c = 20.2100(5) Å, α = 111.182(2) °, β = 111.475(2) °, γ = 100.716(2) °, V = 5275.7(3) Å3; 2: a = 17.2512(7) Å, b = 19.3712(7) Å, c = 19.6248(8) Å, α = 112.803(3) °, β = 105.969(3) °, γ = 100.183(3) °, V = 5507.08(40) Å3]. ESI‐MS studies show that the bismuth oxido clusters 1 and 2 are more easily desolvated as reported for the dmso adduct A. Collision‐induced dissociation (CID) experiments on the solvent free cluster ions reveal a new fragmentation path for the methacrylate ligands. They split into C3H4 fragments as the leaving group and a formate remains bound at the cluster core. Bismuth particles are formed after annealing of 1 at 300 °C, whereas a composite consisting of Bi/β‐Bi2O3/C was formed in the temperature range of 400 °C to 600 °C. Calcination of 1 at 300 °C and 400 °C provided the formation of an amorphous material containing bismuth and a composite composed of β‐Bi2O3/Bi2O2CO3/Bi/C, respectively. At higher calcination temperatures, α‐Bi2O3 was obtained. The decomposition products do not show any sulfate incorporation as observed for A.

From a Cerium-Doped Polynuclear Bismuth Oxido Cluster to β-Bi2O3:Ce

“…In order to complement the above-mentioned analyses, an ESI-MS spectrum of the orange crystals of 1 dissolved in DMSO/MeCN (0.05:0.95, v/v) was recorded. Earlier, ESI-MS was shown to be a useful method in the characterization of the composition of polynuclear bismuth oxido clusters and to prove their stability in the gas phase. ,− The ESI-MS spectrum of 1 shows the typical [Bi 38 O 45 (NO 3 ) 21 (DMSO) y ] 3+ and [Bi 38 O 45 (NO 3 ) 20 (DMSO) y ] 4+ clusters with common charge states, which are known from the former work of Sattler et al (Figure S4). Furthermore, a [Bi 38 O 45 (NO 3 ) 19 (DMSO) y ] 5+ charge state is detected.…”

Photocatalytic water purification under visible light using carbon nitride materials and β-Bi2O3 immobilized on electrospun polyvinyl acetate fibers

“…Detailed information on synthesis and characterization of the CN photocatalyst materials was reported in reference [50]. To obtain β-Bi 2 O 3 , the [Bi 38 O 45 (OMc) 24 (EtOH) 13 ] cluster was synthesized according to reference [47] and hydrolyzed to obtain pure β-Bi 2 O 3 according to [26,51]. Detailed information about the characterization of these materials are given in [26,51] and SI 1.…”

Anchoring Atomically Precise Chiral Bismuth Oxido Nanoclusters on Gold: The Role of Amino Acid Linkers

“…Another approach might be realized using chiral atomically precise metal oxido nanoclusters (MO-NCs) as chiral light absorbers. Especially, we are interested in bismuth-based compounds because this element shows a large pool of accessible MO-NCs, with the option of their targeted optical absorption tuning via a recently developed doping procedure. − In addition, the environmentally benign nature of bismuth compounds offers access to novel sustainable materials and medical applications and led already to developments with potential application, e.g., in catalysis, medicine, and electronics. − Among the bismuth oxido nanoclusters (BiO-NCs), those with a [Bi 38 O 45 ] 24+ core seem to be the most stable ones, as evidenced by studies on various accessible BiO-NCs of this structure type covered with different ligands such as sulfonates, carboxylates, and nitrate. − Furthermore, their physical properties such as the optical band gap can be tuned by doping the cluster core for example with rare earth elements . However, many of the BiO-NCs suffer from either low hydrolytic stability at the ligand periphery, low solubility, low biocompatibility of their ligands, or accessibility on a large scale. , Recently, we were able to prepare a rather stable and highly soluble amino acid-modified BiO-NC of the type [Bi 38 O 45 (Boc- l -Phe-O) 24 (dmso) 9 ] ( 1 ) and studied its deposition behavior using different coating techniques on gold surfaces.…”