Self-assembly directed by C–H activation: Synthesis and characterization of [(Cp∗Ir)2(R–Ndouble bond; length as m-dashC–Ph–Cdouble bond; length as m-dashNR)]2(4,4-bipyridine)2·(OTf)4 (R = Ph, Me)

Self-assembly of a novel class of bis-imine-cyclometalated macrocycles [(Cp∗Ir)2(Ph–Ndouble bond; length as m-dashC–Ph–Cdouble bond; length as m-dashN–Ph)]2(4,4′-bipyridine)2·(OTf)4 (3a) and [(Cp∗Ir)2(Me–Ndouble bond; length as m-dashC–Ph–Cdouble bond; length as m-dashN–Me)]2(4,4′-bipyridine)2·(OTf)4 (3b) was directed by double-site C–H activations of aromatic bis-imine substrates. Two synthetic routes were established, using either (i) binuclear cyclometalated complexes (Cp∗Ir)2L1Cl2 (1a) and (Cp∗Ir)2L2Cl2 (1b) or (ii)4,4′-bipyridine(bpy)-bridged complex (Cp∗IrCl2)2(bpy) (2) as starting materials. All the products were characterized by IR, 1H NMR and EA. Isomers were found in macrocyclic complexes, which were thermodynamically stable from reversible transformation in days. Highly robust structure of the cyclometalated macrocycles was indicated by the existence of stable isomer pairs. One isomer of 3b was determined by single-crystal X-ray diffraction. It was a rare case for half-sandwich metallosupramolecular macrocycles that weak interactions between macrocycles and OTf ions were fully captured in detail, and were demonstrated to be essential for the maintenance of tunnel structures of macrocycles in crystal packing.