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

James P. Coliman, Anthony O. Chong, Geoffrey B. Jameson, Richard T. Oakley, Eric Rose, Eric R. Schmittou, James A. Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

139 Scopus citations

Abstract

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)C1 (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 length (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 C2H-Pije, a = 11.878 (6) Å, b = 13.304 (7) Å, c = 23.725 (13) Å, β = 114.60 (2)° at -140 °C; Z = 2. Å crystallographic center of symmetry is imposed on the dimer. The structure was refined on all data including F02 < 0 (4663 observations) to values for R and Rv on F1 of 0.103 and 0.152. For the portion of data having F02 > 3σ(F02) (3213 observations) the values for R and Rw 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 Å. The Cu-Cu separation is 6.332 (4) A and the interplanar separation of the two porphyrin rings is 3.87 Å. In solution at ambient temperatures, conformational changes involving motions of the two porphyrin rings cause considerable line broadening in the NMR spectra of all 5,15-bridged dimers. However, at temperatures above 90 °C conformational equilibria are sufficiently rapid to produce well-resolved spectra.

Original languageEnglish (US)
Pages (from-to)516-533
Number of pages18
JournalJournal of the American Chemical Society
Volume103
Issue number3
DOIs
StatePublished - Feb 1981

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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