Impact of the Exchange of the Coordinating Solvent Shell in [Bi 38 O 45 (OMc) 24 (dmso) 9 ] by Alcohols: Crystal Structure, Gas Phase Stability, and Thermoanalysis

Recrystallization of the bismuth oxido cluster [Bi 38 O 45 (OMc) 24 (dmso) 9 ] · 2dmso · 7H 2 O ( A ) (OMc = O 2 C 4 H 5 ) from alcohols such as EtOH and i PrOH gave single crystals of the bismuth oxido clusters [Bi 38 O 45 (OMc) 24 ( R OH) x (H 2 O) y ] [ R = Et, x = 13, y = 0 ( 1 ); R = i Pr, x = 10, y = 2 ( 2 )]. Both compounds crystallize in the triclinic space group P 1 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) Å 3 ; 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) Å 3 ]. 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 C 3 H 4 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‐Bi 2 O 3 /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‐Bi 2 O 3 /Bi 2 O 2 CO 3 /Bi/C, respectively. At higher calcination temperatures, α‐Bi 2 O 3 was obtained. The decomposition products do not show any sulfate incorporation as observed for A .