Z12-acetate synthesis. A 20 mL vial was equipped with a septum and cycled three times between argon and vacuum. Zirconium propoxide (2.25 mL, 5 mmol, 1 eq.) was added to the vial, together with dry DCM (5.463 mL). Under stirring, distilled acetic acid (2.287 mL, 40 mmol, 8 eq.) was injected, reaching a total reaction volume of 10 mL and thus a zirconium concentration of 0.5 M. After 12 hours at room temperature (19-24°C), the crystalline powder is isolated by filtration and further washed with 50 mL of a DCM:acetic acid mixture (4:1). Finally, the white powder is dried overnight under high vacuum. The powder is stored in a dessicator. to maintain a Zr concentration of 0.5 M. After stirring 24 hours at 30 °C the clusters were purified. The butanoate capped cluster was purified by evaporating the solvent using the Schlenk line after which a white waxy solid is obtained. Acetonitrile (15 mL) was added and the clusters were macerated overnight. After centrifugation 4 minutes at 5000 rcf the supernatant is discarded and the clusters are dried on the Schlenk line for 24h yielding a white solid. For hexanoate and octanoate clusters the solution was divided over 2 large centrifuge tubes (± 5 mL reaction mixture in each) and acetonitrile (10 mL) was added to each centrifuge tube in order to precipitate the clusters. Via centrifugation (5000 rcf, 4 min), the cluster (viscous oil) was separated from the supernatant and both oils were redissolved in DCM (1 mL). To each tube 6 mL acetonitrile was added to precipitate the cluster. This last step was repeated twice and finally, the clusters were dried overnight under vacuum. Zr12-hexanoate was obtained as a waxy solid and Zr12-octanoate was obtained as a viscous liquid. Zr12-butanoate was obtained with a yield of 49 %. Zr12-hexanoate was obtained as a waxy solid with a yield of 71 %.Zr12-octanoate was obtained as a viscous oil with a yield of 52.3 %.