Expanded porphyrins have received considerable attention due to their unique optical, electrochemical and coordination properties. Here, we report benzene- and pyridine-incorporated octaphyrins(1.1.0.0.1.1.0.0), which are synthesized through Suzuki-Miyaura coupling of α,α'-diboryltripyrrane with m-dibromobenzene and 2,6-dibromopyridine, respectively, and subsequent oxidation with 2,3-dicyano-5,6-dichlorobenzoquinone. Both octaphyrins are nonaromatic and take on dumbbell structures. Upon treatment with Pd(OOCCH), the benzene-incorporated one gives a C symmetric NNNC coordinated bis-Pd complex but the pyridine incorporated one gives C and C symmetric NNNC coordinated bis-Pd complexes along with an NNNN coordinated bis-Pd complex bearing a transannular C-C bond between the pyrrole α-positions. In addition, these two pyridine-containing NNNC Pd complexes undergo trifluoroacetic acid-induced clean interconversion.
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