Giant Electroactive M₄L₆ Tetrahedral Host Self-Assembled with Fe(II) Vertices and Perylene Bisimide Dye Edges

Self-assembly of octahedral Fe(II) ions and linear perylene bisimide (PBI) dyes with 2,2'-bipyridine groups covalently attached at the imide positions quantitatively yields an Fe4(PBI)6 tetrahedron by the directional bonding approach. With an edge length of 3.9 nm and estimated internal volume >950 Å(3), tetrahedron T is one of the largest M4L6 tetrahedra ever reported. Importantly, many of the desirable photo- and electroactive properties of the PBI ligands are transferred to the nanoscale metallosupramolecule. Tetrahedron T absorbs strongly across the visible spectrum out to 650 nm and exhibits a total of 7 highly reversible electrochemical oxidation and reduction waves spanning a 3.0 V range. This facile cycling of 34 electrons between +18 and -16 charged species is likely enabled due to the porous nature of the tetrahedron that allows the necessary counterions to freely flow in and out of the host. Host-guest encapsulation of C60 by T in acetonitrile was studied by (13)C NMR spectroscopy, UV-vis spectroscopy, and ESI-MS, confirming that the tetrahedron is a suitable host for large, functional guest molecules.