Alternatively Connected Corrole‐Porphyrin Multimetallic Complexes: Synthesis, Structure, and Properties

Abstract Synthetic multimetallic porphyrinoids are potential candidates in catalysis, molecular magnetism and as modern optoelectronic materials. Introducing electronic heterogenity in these multi‐porphyrinoids shall bring in novel electronic and redox characteristics. In this direction, herein we report four discrete Corrole‐Porphyrin‐Corrole C[10] ⋅ P[5,15] ⋅ C[10] hybrids that have both corrole and porphyrin units covalently connected together. Metal ions in diverse oxidation states have been incorporated into respective cores to achieve homo and heterotrinuclear metal complexes. Selective metalation at the porphyrin and corrole cores was achieved by step‐wise insertion of Zn(II)/Cu(II), Zn(II)/Ga(III) and Cu(II)/Cu(II) ions to suit the dianionic and trianionic pockets, respectively. Single crystal X‐ray diffraction studies reveal the solid‐state structural evidence for both homo‐, and hetero‐trinuclear metal complexes. The Zn(II) and Ga(III) moieties have two distinct geometries in the molecular assembly. The geometry of Zn(II) at the porphyrin core is a perfect square planar, whereas the Ga(III) geometry at the corrole is square pyramidal with pyridine as an axial ligand. In case of homotrinuclear Cu(II) complex, the Cu(II) ions adopt square planar geometry irrespective of the core. Similar to all porphyrin trimers, C[10] ⋅ P[5,15] ⋅ C[10] trimers exhibit significant excitonic coupling between corrole and porphyrin units in the absorption spectra. The cyclic voltametric investigations also reveal electronic coupling between the individual chromophores despite the non‐coplanar arrangement amongst the individual macrocycles.