Ruthenocenoporphyrinoids─π-Conjugation Transmitted across 1,3-Substituted Ruthenocene.

Abstract

Synthesis of ruthenocenoporphyrinoids, wherein the [RuCp*]⁺ moiety coordinates to the cyclopentadienyl π-surface of the 21-carba-23-selenaporphyrin macrocyclic platform, has been developed. The specific electronic ruthenocene-macrocycle communication is observed. The macrocyclic ring current is maintained despite the strong π-conjugation in the cyclopentadienyl ring of the ruthenocene fragment. The theoretical data are consistent with the magnetic properties reflected by ¹H NMR spectra. DFT-optimized molecular models were used to evaluate the NICS 2D maps and EDDB plots. These data gave an insight into the aromaticity and effectiveness of π-conjugation across 1,3-substituted ruthenocene in the obtained hybrid molecules.