Dirhodium(II,II)-porphyrin-based multiredox systems were easily prepared by combining the versatile reactivity, both axial and equatorial, of the [Rh 2 (form) 2 (O 2 CCF 3 ) 2 (H 2 O) 2 ] (form = N,NЈ-di-p-tolylformamidinate) complex and the wellknown coordination capability of meso-substituted phenylporphyrins. In this way, redox systems featured by porphyrins axially or equatorially coordinated to the dirhodium subunits were obtained. Electrochemical and luminescence properties of the new assemblies were also investigated. Porphyrin-dirhodium(II,II) multiredox assemblies were synthesized by exploiting both the classical axial and the peculiar equatorial reactivity of the complex
The species [Rh 2 (form) 2 (PCOO) 2 ] (2), featuring two bridged (carboxyphenyl)porphyrins in the equatorial positions, was prepared by metathetical reaction of 1 with the sodium salt of meso-5-(4-carboxyphenyl)-5,10,15-triphenylporphyrin (PCOO). Conversely, redox systems in which porphyrins are axially ligated to dirhodium were obtained by treating 1 with a variety of functionalized meso-pyridylporphyrins. Depending on the number and position of the peripheral pyridyl substituents, assemblies with different nuclearity, both in terms of metal and porphyrin subunits, were isolated. The 1:2 dirhodium/porphyrin adduct, [Rh 2 (form) 2 (O 2 CCF 3 ) 2 -(PyP) 2 ] (3) was obtained by treatment of 1 with triphenyl(pyr- [a]