The use of N-salicylidene-2-amino-5-chlorobenzoic acid as a ligand in Ni(ii) chemistry has afforded a Ni₂₆ cluster with a ‘rabbit-face’-like topology, as well as a Ni₁₈ compound with an unusual ‘molecular chain’ structure.

Changes of the solvent and organic ligand substituents in a general reaction system have led to three Ni^II₄ clusters with different topologies and magnetic responses.

The reaction of Dy(O₂CMe)₃·xH₂O and Ga(NO₃)₃·xH₂O led to the isolation of (ⁿBu₄N)[Ga^III ₈Dy^III(OH)₄(shi)₈] (1). The compound possesses a unique chemical structure enclosing the central magnetic Dy^III ion between diamagnetic Ga^III-based metallacrown 12-MC-4 ligands. The double-decker complex exhibits field-induced single-molecule magnet (SMM) behaviour with an effective energy barrier (U_eff) of 39 K (27.1 cm⁻¹). Consistent with the observed slow relaxation of magnetization, theoretical calculations suggest a ground state mainly determined by |±11/2> in the easy axis direction.

The first use of N-salicylidene-2-amino-5-chlorobenzoic acid in metal cluster chemistry has afforded a new Ni^II₁₁ cage consisting of Ni₄ squares and Ni₃ triangles.

A new family of complexes (^tBu₄N){[Ln^III(O₂CBu^t)₄][12-MC-_{Mn(III)N(shi)}-4]}·5CH₂Cl₂ (Ln = Gd (1) and Tb (2)), (^tBu₄N)₂{[Y^III(O₂CBu^t)₄][12-MC-_{Mn(III)N(shi)}-4]}(ClO₄) (3); where shiH₃ = salicylhydroxamic acid; Bu^tCO₂⁻ = pivalate ions; ^tBu₄N = tetrabutylammonium and ClO₄⁻ = perchlorate ions, has been isolated. The reaction of salicylhydroxamic acid with Mn(O₂CBu^t)₂·2H₂O, Ln(NO₃)₃·xH₂O, ^tBu₄NClO₄ in the presence of morpholine (C₄H₉NO) led to the isolation of compounds 1–3. The complexes belong to the 12-MC-4 family of Metallacrowns (MCs) possessing a central {Mn₄^IIILn^III(µ-NO)₄}¹¹⁺ core with the four Mn^III atoms occupying the periphery positions, while the formed [Mn–N–O] repeating unit, assists in the accommodation of the Ln^III atom in the center of the ring. Peripheral ligation is provided by four η¹:η¹:μ pivalate ions. Direct current magnetic susceptibility (dc) measurements revealed the presence of predominant antiferromagnetic exchange interactions within the metal centers. A 1-J fitting model was used in order to quantify the Mn^III–Mn^III interactions and fitting of the data, for the diamagnetic Y^III analogue, gave J = −3.74 cm⁻¹ and g_Mn(III) = 2.07. Fitting of the {Mn₄Gd} compound using a 2-J model, counting additionally for the Mn^III–Gd^III interactions, revealed values of J₁ = −3.52 cm⁻¹, J₂ = −0.45 cm⁻¹, and g_Mn(III) = 1.99.

A novel family of combined 9-MC-3/12-MC-4 {Fe₆Ln} metallacrown-like complexes or else a new form of metallacryptates is reported, while the {Fe₆Dy} analogue shows SMM behavior.