| 總結: | Out-of-plane deformations of metalloporphyrin skeletons have been well documented as playing important roles in relevant biological processes. In contrast, out-of-plane binding to the N-core of large metal cations as period 6 post-transition elements has remained poorly investigated. We describe herein monometallic complexes of Pb(II) and Bi(III) with 5,10 single strapped porphyrin ligands bearing a carboxylic acid group with two possible “in/out” orientations, in which the metal ions are bound to the N-core of the macrocycle either from the strap side or from the naked side. In the case of Pb(II), both the kinetics of insertion and resulting OOP stereoselectivity are influenced by the “in/out” stereoisomerism of the overhanging COOH. Remarkably, Bi(III) insertion proceeded quasi-instantaneously at RT owing to the transmetalation of its Pb(II) counterpart. The addition of a cyano group in ${\alpha }$ position of the carboxylic acid group generates a ligand exhibiting an increased stereoselectivity in the metalation processes with Pb(II) and Bi(III): these cations are coordinated exclusively from the naked and strap side of the macrocycle, respectively. This difference in behavior is likely explained by steric hindrance for the divalent cation, which is counterbalanced by the establishment of the second sphere of coordination with the strap for the trivalent cation. Such a behavior is thought of interest for the further design of adaptable supramolecular coordination assemblies.
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