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Heterobimetallic [Ni(salen)Ln(hfa)3] species [H2salen and Hhfa being N,N′‐ethylenebis(salicylideneimine) and hexa‐fluoroacetylacetone respectively], where Ni(salen) acts as a neutral chelating ligand towards LnIII, form a series of isostructural compounds for Ln = YIII and any lanthanideIII cation from La to Yb. They are also isostructural with some of the [Cu(salen)Ln(hfa)3] compounds. They sublime without decomposition under vacuum which makes them potential single‐source precursors in MOCVD. Sublimation, thermal behaviour, pressure and composition of the vapour phase versus temperature have been studied for the yttrium derivative, by means of thermal analyses, and mass spectrometry using a Knudsen cell. The dissociation process [Ni(salen)Y(hfa)3] = Ni(salen) + Y(hfa)3 has been thermodynamically investigated. Information on the solid‐state intermolecular interactions in relation with volatility was obtained through the crystal structure determination of the gadolinium derivative. A comparative structural study of [Ni(salen)Gd(hfa)3] and [Cu(saloph)Y(hfa)3], [H2saloph is N,N′‐o‐phenylenebis(salicylideneimine)], allows to under‐stand why the latter is less volatile than the former despite similar molecular and solid‐state structures.

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The heterotrimetallic species [Ni(acacen)KLa(pta)4] [H2acacen and Hpta being N,N′‐ethylenebis(acetylacetonimine) and 1,1,1‐trifluoro‐5,5‐dimethyl‐2,4‐hexanedione, respectively] was obtained by interaction of Ni(acacen) with KLa(pta)4 in chloroform. From the X‐ray, single crystal structure determination, the potassium cation acts as a bridge between the complex anion [La(pta)4]− and the neutral complex Ni(acacen). Sublimation, thermal behaviour, pressure, and composition of the vapour phase have been investigated for both [Ni(acacen)KLa(pta)4] and the parent complexes Ni(acacen) and KLa(pta)4, by means of thermal analysis and mass spectrometry using a Knudsen cell. The heterotrimetallic molecule was not found in the saturated vapour. Two processes take place upon heating: [Ni(acacen)KLa(pta)4](s) → [KLa(pta)4](s) + Ni(acacen)(g) and [KLa(pta)4](s) → [KLa(pta)4](g). The standard free energy of formation for [Ni(acacen)KLa(pta)4] have been estimated (ΔGf0 380K = −6.1±2 kJ/mol). [Ni(acacen)KLa(pta)4] can be sublimed completely at low pressure because both parent complexes KLa(pta)4 and Ni(acacen) are volatile.

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