Abstract
In order to allow estimation of the electrostatic and dipolar contributions to the cohesive forces in volatile lanthanide β‐diketonates, these compounds are considered to be purely ionic. The relevant lattice sums can then be computed directly and underestimation of the ionic contributions is avoided. Even without considering the effect of shielding by bulky substituents, the calculations, based on crystallographic results, show that the electrostatic contributions to lattice forces are negligible and do not influence the volatility. The electrostatic stabilization of the dimers, known to occur in the case of some chelates of 2,2,6,6‐tetramethyl‐3,5‐heptanedione, is, however, sufficient to account for the observed trends in heats of vaporization, heats of sublimation, and gas chromatographic retention times.

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