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10-Porphyrin Nanorings with Copper(II) and Zinc(II) Centres

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Electronic Communication in Heterometallated Porphyrin Oligomers

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Abstract

The affinity of copper(II) porphyrins for pyridine ligands is extremely weak, but oligo-pyridine templates can be used to direct the synthesis of Cu-containing cyclic porphyrin oligomers when they also contain zinc porphyrins. Here we describe the synthesis of a heterometallated 10-porphyrin nanoring prepared from a Zn/Zn/Cu/Zn/Zn pentamer. The macrocycle has copper porphyrins at two specific positions across the diameter of the ring and zinc porphyrins at the other sites. The Zn/Zn/Cu/Zn/Zn linear porphyrin pentamer binds strongly to a penta-pyridyl template, despite the weakness of the Cu–N interaction, due to of the chelate cooperativity of the neighbouring Zn–N coordinations. The stabilities of a family of four linear porphyrin pentamer complexes were determined by UV-Vis-NIR titrations and analysed using a chemical double-mutant cycle. The results show that the binding energy of the copper centre to an axial pyridine ligand is −6.2 kJ mol−1 when the entropy cost of bringing together the two molecules has already been paid by pyridine-zinc interactions. The development of template-directed approaches in the synthesis of nanorings with combinations of different metals around the ring opens up many possibilities for controlling the photophysical behaviour of these supramolecular systems and for probing their conformations by EPR.

Parts of this chapter have been reproduced from:

Nanorings with copper(II) and zinc(II) centers: forcing copper porphyrins to bind axial ligands in heterometallated oligomers

J. Cremers, S. Richert, D. V. Kondratuk, T. D. W. Claridge, C. R. Timmel, H. L. Anderson, Chem. Sci. 2016, 7, 6961–6968 (Published by The Royal Society of Chemistry. License type CC BY 3.0. https://pubs.rsc.org/en/content/articlelanding/2016/sc/c6sc01809b).

Exploring template-bound dinuclear copper porphyrin nanorings by EPR spectroscopy

S. Richert, J. Cremers, H. L. Anderson, C. R. Timmel, Chem. Sci. 2016, 7, 6952–6960 (Published by The Royal Society of Chemistry. License type CC BY-NC 3.0. https://pubs.rsc.org/en/content/articlelanding/2016/sc/c6sc01810f).

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  1. Department of Chemistry, University of Oxford, Oxford, UK

    Jonathan Cremers

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Cremers, J. (2020). 10-Porphyrin Nanorings with Copper(II) and Zinc(II) Centres. In: Electronic Communication in Heterometallated Porphyrin Oligomers. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-39101-0_2

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