Porphyrin–Polyyne [3]- and [5]Rotaxanes

Abstract

Porphyrin–polyyne [3]- and [5]rotaxanes have been synthesized by condensing aldehyde–rotaxanes with pyrrole or dipyrromethane. The crystal structure of a [3]rotaxane shows that the macrocycles adopt compact conformations, holding the hexaynes near the porphyrin core, and that the phenanthroline units form intermolecular π-stacked dimers in the solid. Fluorescence spectra reveal singlet excited-state energy transfer from the threaded hexayne to the porphyrin, from the phenanthroline to the porphyrin, and from the phenanthroline to the hexayne.

Heteroleptic copper phenanthroline complexes in motion: From stand-alone devices to multi-component machinery

“…3). Copper(I) phenanthroline-based rotaxanes have been made using an analogous template approach and both motions, shuttling and pirouetting, have been demonstrated by several groups [7][8][9][10][11]. The first example, with the macrocycle moving along the thread [12], was reported by Sauvage in 1997, while the pirouetting rotaxane was developed in 1999 [13].…”

Syntheses, Structures, and Spectroscopic Properties of 1,10‐Phenanthroline‐Based Macrocycles Threaded by PtC8Pt, PtC12Pt, and PtC16Pt Axles: Metal‐Capped Rotaxanes as Insulated Molecular Wires

“…Anderson has carried out “active metal template” rotaxane syntheses with different types of metal containing alkynes, for example, zinc porphyrins with ethynyl groups in the meso positions . He has also tethered zinc porphyrins to the macrocyclic components . Leigh and Saito have extended this protocol to other templating metals (Pd, Ni) and types of carbon–carbon bond forming reactions, such as click and Sonogashira cross couplings.…”

Porphyrin‐Containing Rotaxane Assemblies

“…In somewhat related examples various reports groups of Goldup, Anderson, and Qu have both made use of facile substitution and good orientation properties of porphyrins for the assembly of [5]rotaxanes. Figure shows the [5]rotaxane 22 from the Goldup research group, assembled using a copper(I) mediated active‐metal approach which allowed the synthesis of this [5]rotaxane in a remarkable 70 % yield .…”