Synthesis of "Face to Face" Porphyrin Dimers Linked by 5,15-Substituents: Potential Binuclear Multielectron Redox Catalysts

Article abstract of DOI:10.1021/ja00393a007

As part of the development of binuclear transition-metal complexes capable of facilitating multielectron redox reactions of small molecules (such as O2 and N2), we have devised an efficient and synthetically flexible route to 5,15-disubstituted porphyrins which affords multigram quantities of isomerically pure porphyrins without recourse to chromatography.The 5,15-substituents are principally amine ((CH2)_nNHR (n = 1, 2, 3; R = H, CH3)) and acid chloride ((CH2)_nC(O)Cl (n = 1, 2)) groups.Reactions of the two types of substituted porphyrins lead to a new class of "face to face" porphyrins with interporphyrin amide bridges of varying lenght (4-7 atoms).An amine-linked dimer has been produced by the reduction of an appropriate amide linkage.Purely hydrocarbon-linked dimers have also been prepared by the direct coupling of bis(dipyrrylmethanes) bridged by aliphatic (CH2)_n (n = 4, 6) chains.The dimeric porphyrin compounds have been fully characterized by their visible and NMR spectra.The crystal and molecular structure of the bis(copper(II)) complex of one of the amide-linked dimers, the first such determination of a "face to face" porphyrin, is reported.Crystal data for Cu2C74N10O2H86*2H2O*C7H8: space group <*>-P2₁/c; a = 11.878 (6) Angstroem, b = 13.304 (7) Angstroem; c = 23.725 (13) Angstroem, β = 114.60 (2) deg at -140 deg C; Z = 2.A crystallographic center of symmetry is imposed on the dimer.The structure was refined on all data including <*> < 0 (4663 observations) to values for R and R_w on F² of 0.103 and 0.152.For the portion of data having <*> > 3?(<+>) (3213 observations) the values for R and R_w on F are 0.063 and 0.073.The spectral properties of these new porphyrin dimers are discussed with reference to the structural analysis.A striking feature of the structure is a shear-like displacement of one porphyrin unit with respect to the other by an average distance of 4.95 Angstroem.The Cu...Cu separation is 6.332 (4) Angstroem and the interpalanar separation of the two porphyrin rings is 3.87 Angstroem.In solution at ambient temperatures, conformational changes involving motions of the two porphyrin rings cause considerable line broadening in the 1H NMR spectra of all 5,15-bridged dimers.However, at temperatures above 90 deg C conformational equilibria are sufficiently rapid to produce well-resolved spectra.