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Issue 40, 2018
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Self-assembly of porphyrin hexamers via bidentate metal–ligand coordination

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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

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Publication details

The article was received on 20 Apr 2018, accepted on 04 Jun 2018 and first published on 04 Jun 2018


Article type: Paper
DOI: 10.1039/C8DT01572D
Dalton Trans., 2018,47, 14277-14287

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    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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