A series of custom-designed, high yield, isoskeletal tetranuclear Zn/4f coordination clusters showing high efficiency as catalysts with low catalytic loadings in Friedel–Crafts alkylation are described for the first time. The possibility of altering the 4f centers in these catalysts without altering the core topology allows us to further confirm their stability via EPR and NMR, as well to gain insights into the plausible reaction mechanism, showcasing the usefulness of these bimetallic systems as catalysts.

A series of heterometallic coordination clusters (CCs) [Ni^II₂Ln^III₂(L1)₄Cl₂(CH₃CN)₂] 2CH₃CN [Ln = Y (1Y), Sm (1Sm), Eu (1Eu), Gd (1Gd), or Tb (1Tb)] were synthesized by the reaction of (E)-2-(2-hydroxy-3-methoxybenzylidene-amino)phenol) (H₂L1) with NiCl₂·6(H₂O) and LnCl₃·x(H₂O) in the presence of Et₃N at room temperature. These air-stable CCs can be obtained in very high yields from commercially available materials and are efficient catalysts for the room-temperature domino ring-opening electrocyclization synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere. Structural modification of the catalyst to achieve immobilization or photosensitivity is possible without deterioration in catalytic activity.

The employment of three structurally related Schiff bases H₂L1, H₂L2, and H₃L3 with zinc and lanthanide salts under various reaction conditions, gave four families of compounds formulated as [Zn^II₂Ln^III₂(L1)₄(EtOH)₆][ClO₄]₂ (1–3), [Zn^II₅Ln(OH)(L1)₆(H₂O)] (4–6), [Zn^II₄Ln^III₂(OH)₂(L2)₄ (OAc)₂(NO₃)₂(DMF)₃]·DMF (7–9), and [Zn^II₂Ln^III₂(L3)₂(NO₃)₂(CO₃)₂(CH₃OH)₂] (10–12) with robust and novel topologies. Synthetic aspects are discussed. A comprehensive topological analysis of all reported Zn^II/Ln^III CCs with a core nuclearity of four and above is presented and identifies that families (4–6) and (7–9) are the first examples of the 2,3,4M6–1 motif in Zn^II/Ln^III chemistry. Magnetic studies are presented for the Dy^III analogues (1, 7, and 10) are presented, 7 demonstrates field-induced slow relaxation of the magnetization. Fluorescence studies are also discussed.

The aim of this perspective is to summarise the use of the reported 3d–4f Coordination Clusters (CCs) in catalytic reactions and to demonstrate the potential of this emerging field. The pioneering work of Shibasaki, Matsunaga and others, demonstrated the use of 3d–4f in situ systems to catalyse asymmetric organic transformations. Our recent studies show that well characterised 3d–4f CCs catalyse numerous organic transformations and useful mechanistic aspects of their catalysis can be obtained. Furthermore, we have shown that by manipulation of the metal ion coordination environment; the nature of the 3d and lanthanide ions and the organic periphery of the ligand can all improve the efficacy of a 3d–4f CC catalyst. All in situ formed and well characterized 3d–4f CCs involved in catalysis are discussed.