To compare the volatilization features of the different Mn compounds, stepped isothermal studies were performed to determine the 1 Torr vapor pressure. A summary of the important thermal properties is given in Table (top). The corresponding TG curves of the all-nitrogen coordinated compounds and mixed O/N-coordinated complexes are depicted in Figure . Additional data on the thermal analysis with the respective DSC curves are provided in the SI. The all-N coordinated compounds (I-VII) exhibit strongly varying TG profiles indicating thermally stable compounds with a clean evaporation behavior and in some cases, compounds tend to decompose during heating. While all the manganese-acetamidinates and the t Bu-formamidinate (compound I, II and IV) feature a very similar one step evaporation with equal onsets of volatilization (Tvol; after 1% mass loss) of 115 °C and onsets of vaporization (Tvap; tangent method) between 174°C and 176°C, the other all-nitrogen complexes are thermally usntable as seen by multiple steps indicating decomposition resulting in residual masses between 24.1 % and 30.0 %. On the contrary, compounds I, II and IV are associated with one-step evaporation with lower residual masses (in the range 4.6 % and 8.1 %) indicating a high thermal stability. The dinuclear compounds I and IV reveal much higher melting points of 137 °C and 175 °C, respectively, while the mononuclear compound II already melts at 107 °C. In contrast to the all-nitrogen coordinated complexes, the mixed O/N coordinated complexes exhibit a higher thermal stability which is evident by the one step evaporation of most of the complexes (ßI, ßIII, ßIV) and the low residual masses between 1.3 % and 3.6 %. Taking into consideration the onset temperature of volatilization, higher volatility of the ß-ketoiminates was observed in comparison to the all-N coordinated complexes. Interestingly, the volatility does not follow the expected trend of increasing volatility with decreasing substituent size of the ligand The comparison of the onsets of volatilization and vaporization reveal a trend for the mononuclear compounds ßIII and ßIV with Tvol.= 83.5°C , Tvap.= 201°C and Tvol.= 96°C , Tvap.= 228°C, respectively. An unusual opposite trend was observed for compounds ßI and ßII, as even Tvol (Tvol ßI = 93°C; Tvol ßII = 83°C) as also Tvap (Tvap ßI = 247°C; Tvap ßII = 222°C is higher for methyl derivate ßI. A plausible explanation for this observation could be the dinuclear solid state nature of compound ßII and the associated higher molecular mass. The small step in the TG trace could be explained by a partial decomposition of this dinuclear molecule, which besides the lower volatility indicates the poor thermal properties of this compound. An even lower volatility is observed for compound ßI. From the observations made above, compounds ßIII and ßIV exhibit the most promising thermal properties for the mixed O/N-coordinated complexes. To investigate the evaporation behavior and the volatility, stepped isothermal TG experiments were performed for compounds (I), (II), (IV), (ßIII) and (ßIV) as depicted in Figure . Based on these measurements, the vapor pressure and volatilization enthalpies were estimated by the method established by Price et.al. according to the Langmuir and Clausius-Clapeyron equation and the data are tabulated Table . The vapor pressures for the mixed O/N coordinated complexes are higher than the ones of the all-nitrogen coordinated complexes. Also, the difference within the ligand substitution pattern shows a clear trend for the 1 Torr vapor pressures with 172 °C and 207 °C for compound ßIII and ßIV, respectively. For the all-nitrogen coordinated compounds an exception from the expected trend is observable. The resulting values for the vapor pressure and the vaporization enthalpy(ΔHVap) of compound II deviate drastically from the expected trend. This can be explained taking into consideration the vapor pressure plots in Figure which are used to determine the 1 Torr vapor pressure (intersection 1Torr) and the enthalpy of vaporization (slope). The plots are determined by a linear fit of the determined vapor pressures from stepped isothermal gravimetry experiments. The data for compound II show a certain deviation and this can originate from decomposition during the stepped isothermal gravimetry experiment indicating the limited thermal stability over long time periods. In contrast, the two dinuclear compounds (in the solid state) I and IV seem to be much more stable under these conditions. This could be attributed to the higher shielding of the Mn center in the solid state as derived for the SC-XRD experiments. The linear trend of the vapor pressure shift to higher temperature with heavier and more sterical demanding side chains that influence the intermolecular interactions and consequently the vapor pressure. The enthalpy of vaporization of compound IV is much higher with 106.2 kJ/mol in comparison to the enthalpy of vaporization of compound I with 55.2 kJ/mol.