The kinetic lability of hexadentate gallium-based tripods is sufficient to ensure thermodynamic self-assembly of luminescent heterodimetallic [GaLn(L3)3]6+ helicates on the hour time scale, where Ln is a trivalent 4f-block cation. The inertness is, however, large enough for preserving the triplehelical structure when [GaLn(L3)3]6+ is exposed to lanthanide exchange. The connection of a second gallium-based tripod further slows down the exchange processes to such an extent that spectroscopically active [CrErCr(L4)3]9+ can be diluted into closed-shell [GaYGa(L4)3]9+ matrices without metal scrambling. This feature is exploited for pushing molecularbased energy-transfer upconversion (ETU) at room temperature.