Data for 'Fatty acid capped, metal oxo clusters as smallest conceivable nanocrystal prototypes'

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Figure 3: Experimental PDF of zirconium oxo clusters with different capping ligands. The C-C, Zr-O, and Zr-Zr distances are assigned. We make a distinction between the Zr-Zr distances within one Zr6 cluster and the Zr-Zr distances that are characteristic for the dimer

Figure 4: PDF refinement of the Zr12-acetate cluster with various models, derived from the reported crystal structure. 4 The best fit is obtained when including the oxygen and carbon atoms from the acetate ligands. The refined parameters are given in Table S1

Figure 5: PDF refinement for Zr12-butanoate and Zr12-octanoate using the Zr12-acetate structure model. PDF refinement of Zr6- methylbutanoate using the Zr6-acetate structure model. Finally, the PDF refinement of Zr12-oleate using the Zr12-propionate structure model, with or without background correction in reciprocal space. If applied in the refinement, the exponentially dampening sine wave is shown (orange dotted lines). The refined parameters are given in Table S3.

Figure 6: FTIR spectra of Zr12-acetate, -propionate, -hexanoate, -oleate and Zr6-methylheptanoate. The weak band at 1750 cm-1 in the spectrum of Zr12-acetate is assigned to a small amount of acetic acid that is not involved in hydrogen bonding of any kind. 71
An ester impurity is ruled out because of the absence of any signal around 4 ppm in NMR, (see Figure S10).

Figure 7: (A) NMR spectra in CDCl3 of Zr12-acetate, -propionate, -hexanoate, -oleate and Zr6-methylheptanoate. (B) DOSY of the Zr12-acetate cluster with one faster diffusing species and a set of three resonances pertaining to a slowly diffusing species (the cluster)

Figure 8: ESI-HR-MS analysis of the dimeric Zr12-butanoate cluster and of the monomeric Zr6-methylbutanoate cluster. Both the ex- perimental and simulated spectra are shown.

Figure 10: (A) PDF fit for Hf12-acetate, Hf6-methylbutanoate and Hf12-oleate clusters with exponentially dampening sine wave con- tribution. The refined parameters are indicated in Table S9. (B) FTIR spectra of the hafnium oxo clusters synthesized via bottom up.

Figure 11: Catalytic esterification of oleic acid with ethanol, catalyzed by either Zr12-oleate (green) or ZrO2 nanoparticles (gray). In both cases, 10 mol% Zr, with respect to the carboxylic acid substrate, was added.