Abstract (PDF) Graphical Abstract: Four new {Cr8} rings have been synthesized and characterized; they are all based on the classic [CrF(O2CtBu)2]8 ring 1. Three routes have been studied. The first is direct synthesis, by reacting hydrated chromium(III) fluorides with the acid; this has been used to produce [CrF(O2CEt)2]8 3. The second route uses 3 as a precursor and substitute with an incoming carboxylate. This has been used to make [CrF(O2CCCl3)2]84 and [CrF(O2CC6F5)2]85. The third route uses N-ethyl-D-glucamine (H5Etglu) as a template and produces chiral rings [Cr8F4(Etglu)(O2CtBu)15] 6. The single crystal X-ray structures of these new compounds are reported.