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Issue 8, 2018
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Light-initiated reversible conversion of macrocyclic endoperoxides derived from half-sandwich rhodium-based metallarectangles

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Abstract

Although reversible photo-dimerization or oxygenation of anthracene and its derivatives is a common reaction, light-initiated reversible conversion of endoperoxide organometallic frameworks has only rarely been addressed. Herein, a series of tetranuclear organometallic macrocycles, [Cp*2Rh2(μ-C2O4O)]2(BP4VA)2(OTf)4 (4), [Cp*2Rh2(BiBzIm)]2(BP4VA)2(OTf)4 (5), and [Cp*2Rh2(DHBQ)]2(BP4VA)2(OTf)4 (6), were obtained in good yields from the reactions of the binuclear half-sandwich rhodium precursors [Cp*2Rh2(μ-C2O4O)Cl2] (1), [Cp*2Rh2(BiBzIm)Cl2] (2), and [Cp*2Rh2(DHBQ)Cl2] (3) with the 9,10-bis((E)-2-(pyrid-4-yl)vinyl)anthracene (BP4VA) ligand. The photochemical reaction of these metallarectangles was investigated by NMR and UV/vis spectroscopy. We have demonstrated that complexes 4, 5, and 6 can be reversibly and nearly quantitatively converted to the macrocyclic endoperoxides 4-O2, 5-O2, and 6-O2. Meanwhile, the structure of the endoperoxide photoproducts was unambiguously confirmed by 1H/13C NMR spectroscopy, IR spectroscopy, elemental analyses, and X-ray crystallography.

Graphical abstract: Light-initiated reversible conversion of macrocyclic endoperoxides derived from half-sandwich rhodium-based metallarectangles

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Supplementary files

Article information


Submitted
21 Oct 2017
Accepted
24 Jan 2018
First published
24 Jan 2018

Dalton Trans., 2018,47, 2769-2777
Article type
Paper

Light-initiated reversible conversion of macrocyclic endoperoxides derived from half-sandwich rhodium-based metallarectangles

W. Shan, W. Gao, Y. Lin and G. Jin, Dalton Trans., 2018, 47, 2769
DOI: 10.1039/C7DT03962J

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