Issue 40, 2018

Self-assembly of porphyrin hexamers via bidentate metal–ligand coordination

Abstract

The supramolecular assembly of metal-porphyrin hexamers with bidentate ligands in chloroform solutions is demonstrated by UV/Vis and 1H NMR-titrations, and Small Angle Neutron Scattering (SANS) experiments. Titrations of zinc porphyrin hexamer Zn1 with 1,4-diazabicyclo[2,2,2]octane (DABCO) revealed that at a DABCO/Zn1 molar ratio of 3, intermolecular sandwich complexes are formed, which can be considered as “circular-shaped porphyrin ladders”. These supramolecular complexes further aggregate into larger polymeric stacks, as a result of a combination of cooperativity effects, π–π stacking interactions, and chelate effects. The presence of rodlike assemblies in solution, formed by assembly of Zn1 and DABCO, is confirmed by SANS-experiments. Using a model for cylindrical assemblies, curve fitting calculations reveal that rods with an average length of 26 nm and a radius of 30–35 Å were formed, corresponding to columnar stacks of approximately 30 hexamer molecules. In contrast, the metal-free hexamer H21 did not form extended assemblies due to the absence of coordinative intermolecular interactions.

Graphical abstract: Self-assembly of porphyrin hexamers via bidentate metal–ligand coordination

Supplementary files

Article information

Article type
Paper
Submitted
20 ⵉⴱⵔ 2018
Accepted
04 ⵢⵓⵏ 2018
First published
04 ⵢⵓⵏ 2018

Dalton Trans., 2018,47, 14277-14287

Self-assembly of porphyrin hexamers via bidentate metal–ligand coordination

M. C. Lensen, R. J. M. Nolte, A. E. Rowan, W. Pyckhout-Hintzen, M. C. Feiters and J. A. A. W. Elemans, Dalton Trans., 2018, 47, 14277 DOI: 10.1039/C8DT01572D

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