Spherical Inorganic Superfullerenes: Rationalization of Unique Gated Confinement at the Nanoscale

The unique spherical nanocapsules/Keplerates of the type {{(Mo)Mo₅}₁₂M’₃₀} (M’ = {Mo^V₂}, V^IV, Cr^III, Fe^III) (more generally: (pentagon)₁₂(spacer/ligand)₃₀) allow – due to their exceptional structural features and easy variations/derivatizations – versatile chemistry and applications as well as the option to study new phenomena of interdisciplinary interest.[1] In this poster we specially refer on the interesting neutral/charged species of [{(Mo^VI)Mo^VI₅O₂₁(L)₆}₁₂{Fe^III(H₂O)L}₃₀] (L = H₂O/CH₃COO^-/Mo₂O_8/9^n-) 1a/type[2] not only because of their tremendous unusual magnetic properties which exhibit spherical networks based on corner-shared M’₃ triangles causing geometrical frustration analogous to that of the planar Kagomé lattices but also for their behavior as unique weak polyprotic acids owing to the external water ligands attached to the M’ metal centers. In the second part we refer to the fact that the capsule [{(Mo^VI)Mo^VI₅O₂₁(H₂O)₆}₁₂{Mo^V₂O₄(CO₃)}₃₀]^72- 2a[3] containing 30 carbonate ligands is a potential starting reagent for the synthesis of novel capsules with weakly coordination ligands such as fluoride ions [{(Mo^VI)Mo^VI₅O₂₁(H₂O)₅F}₁₂ {Mo^V₂O₄(F)(H₂O)}₃₀]^69- 3a.[4]

Fig. Ball-and-stick representation for the structures of 1a, 2a and 3a

[1] A. Müller, P. Grouzerh, Chem. Soc. Rev., 2012, 41, 7431.

[2] A. Müller, S. Sarkar, S. Q. N. Shah, H. Bögge, M. Schmidtmann, S. Sarkar, P. Kögerler, B. Hauptfleisch, A. X. Trautwein, V. Schünemann, Angew. Chem. Int. Ed., 1999, 38, 3238.

[3] S. Garai, E. T. K. Haupt, H. Bögge, A. Merca, A.Müller, Angew. Chem. Int. Ed., 2012, 51, 10528.

[4] S. Garai, M. Rubčić, H. Bögge, E. T. K. Haupt, P. Gouzerh, A.Müller, Angew. Chem. Int. Ed., 2015, 54, 5879 (VIP paper).