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Issue 21, 2019
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UO22+-mediated ring contraction of pyrihexaphyrin: synthesis of a contracted expanded porphyrin-uranyl complex

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Abstract

A new mixed hexaphyrin, pyrihexaphyrin (0.1.0.0.1.0) (1), was prepared via an acid catalyzed cyclization between 5,5′-(pyridine-2,6-diyl)bis(pyrrole-2-carbaldehyde) (2) and terpyrrole (3). This expanded porphyrin undergoes a ring contraction upon metallation with uranyl silylamide [UO2[N(SiMe3)2]2] under anaerobic conditions followed by purification over basic aluminum oxide exposed to air. The uranyl-contracted pyrihexaphyrin (0.0.0.0.1.0) complex (4) produced as a result contains a unique structural architecture and possesses a formally 22 π-electron globally aromatic periphery, as inferred from NMR spectroscopy, single crystal X-ray diffraction, and computational analyses. Support for the proposed contraction mechanism came from experimental data and DFT calculations. Proton NMR and mass spectroscopic analysis provided the first insight into expanded porphyrin-mediated activation of the uranyl dication (UO22+).

Graphical abstract: UO22+-mediated ring contraction of pyrihexaphyrin: synthesis of a contracted expanded porphyrin-uranyl complex

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Article information


Submitted
01 Apr 2019
Accepted
30 Apr 2019
First published
30 Apr 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 5596-5602
Article type
Edge Article

UO22+-mediated ring contraction of pyrihexaphyrin: synthesis of a contracted expanded porphyrin-uranyl complex

J. T. Brewster, H. D. Root, D. Mangel, A. Samia, H. Zafar, A. C. Sedgwick, V. M. Lynch and J. L. Sessler, Chem. Sci., 2019, 10, 5596
DOI: 10.1039/C9SC01593K

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