Ultra‐small nanoparticles of CeO2 obtained in molecular form, so‐called molecular nanoparticles, have been limited to date to a family whose largest member is of nuclearity Ce40 with a {Ce40O58} core atom count. Herein we report that a synthetic procedure has been developed to the cation [Ce100O149(OH)18(O2CPh)60(PhCO2H)12(H2O)20]16+, a member with a much higher Ce100 nuclearity and a {Ce100O167} core that is more akin to the smallest ceria nanoparticles. Its crystal structure reveals it to possess a 2.4 nm size and high D2d symmetry, and it has also allowed identification of core surface features including facet composition, the presence and location of Ce3+and H+ (i.e. HO−) ions, and the binding modes of the ligand monolayer of benzoate, benzoic acid, and water ligands.
Two new CeIV/O2- clusters, (pyH)8[Ce10-O4(OH)4(O3PPh)12(NO3)12] (1) and [Ce6O4(OH)4(O2PPh2)4(O2CtBu)8] (2), have been prepared that contain P-based ligands for the first time. They were obtained from the reaction of (NH4)2[Ce(NO3)6], PhPO3H2 or...
Ultra‐small nanoparticles of CeO2 obtained in molecular form, so‐called molecular nanoparticles, have been limited to date to a family whose largest member is of nuclearity Ce40 with a {Ce40O58} core atom count. Herein we report that a synthetic procedure has been developed to the cation [Ce100O149(OH)18(O2CPh)60(PhCO2H)12(H2O)20]16+, a member with a much higher Ce100 nuclearity and a {Ce100O167} core that is more akin to the smallest ceria nanoparticles. Its crystal structure reveals it to possess a 2.4 nm size and high D2d symmetry, and it has also allowed identification of core surface features including facet composition, the presence and location of Ce3+and H+ (i.e. HO−) ions, and the binding modes of the ligand monolayer of benzoate, benzoic acid, and water ligands.
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