While TGA is a most valuable tool to initially assess the performance of a precursor candidate, it can be deceptive as the evaporation conditions typically differ from evaporation parameters applied to precursors in CVD and ALD processes. More precisely, TGA only probes a few milligrams of an analyte at atmospheric pressure and not multi-gram quantities under roughing pump vacuum conditions. Additionally, the adjustment of carrier gas flows can have a strong impact on the observed volatilization behavior. Consequently, we probed compounds 1 -12 under more realistic process conditions: 300 mg of each compound were subjected to sublimation at around 1 x 10 -1 mbar at the lowest temperature at which sublimation was observed. The recovered substances were first weighted and then subjected to elemental analysis (EA) to assess their purity compared to non-sublimed reference samples. Table summarizes the respective sublimation temperatures Ts and the bulk sublimation recovery yields alongside the residual masses from TGA and melting points TM obtained from melting point measurements. Expectedly, compounds 1, 9 and 11 which had already demonstrated the best performance in TGA were recovered with high yields ranging from 78 % (9) up to over 90 % (1, 11), whereby the recovered substances EA did not differ from the reference samples (difference in C, H and N content in % smaller than 0.3 %). Likewise, recovered material from compounds 3 and 4 was found to be pure by EA. However, the recovery rates were already significantly lower with around 50 % and 60 % and decomposed material was observed at the bottom of the sublimation set-up. Compounds 2, 6 and 10 were sublimed with low recovery yields and only for 10 the conducted EA was found to not significantly differ from the reference. Samples of 5, 8 and 12 could not be recovered by sublimation as decomposition occurred upon careful and stepwise heat-up to a maximum sublimation temperature of 120 °C. In summary, the suitability of candidates 1, 9 and 11 for CVD as well as ALD applications in terms of their fundamental thermal properties was validated while the sublimation experiments allowed to identify 3 and 4 more clearly as potential CVD precursors. A significant advantage of candidate 9 over all other competitors of the investigated compound series is the absence of silicon in the ligand sphere which render it more appealing for process implementation as e.g. the contamination of metallic cobalt thin films by silicon is unwanted in semiconductor industry. Conclusions: Rational variation of the imido-nitrogen alkyl side chain may allow to selectively alter the physico-chemical properties of the resulting Co(II) complexes so that e.g. the melting point may be reduced and the volatility increased while the overall high thermal stability is maintained.