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Issue 20, 2017
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Characterization and photocatalytic behavior of 2,9-di(aryl)-1,10-phenanthroline copper(i) complexes

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Abstract

The synthesis, characterization, photophysical properties, theoretical calculations, and catalytic applications of 2,9-di(aryl)-1,10-phenanthroline copper(I) complexes are described. Specifically, this study made use of di(aryl)-1,10-phenanthroline ligands including 2,9-di(4-methoxyphenyl)-1,10-phenanthroline (1), 2,9-di(4-hydroxyphenyl)-1,10-phenanthroline (2), 2,9-di(4-methoxy-3-methylphenyl)-1,10-phenanthroline (3), and 2,9-di(4-hydroxy-3-methylphenyl)-1,10-phenanthroline (4). The 2 : 1 ligand-to-metal complexes, as PF6 salts, i.e., ([Cu·(1)2]PF6, [Cu·(2)2]PF6, [Cu·(3)2]PF6, and [Cu·(4)2]PF6) have been isolated and characterized. The structures of ligands 1 and 2 and complexes [Cu·(1)2]PF6 and [Cu·(3)2]PF6 have been determined by single-crystal X-ray analysis. The photoredox catalytic activity of these copper(I) complexes was investigated in an atom-transfer radical-addition (ATRA) reaction and the results showed fairly efficient activity, with a strong wavelength dependence. In order to better understand the observed catalytic activity, photophysical emission and absorption studies, and DFT calculations were also performed. It was determined that when the excitation wavelength was appropriate for exciting into the LUMO+1 or LUMO+2, catalysis would occur. On the contrary, excitations into the LUMO resulted in no observable catalysis. In light of these results, a mechanism for the ATRA photoredox catalytic cycle has been proposed.

Graphical abstract: Characterization and photocatalytic behavior of 2,9-di(aryl)-1,10-phenanthroline copper(i) complexes

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Supplementary files

Article information


Submitted
01 Feb 2017
Accepted
11 Apr 2017
First published
12 Apr 2017

Dalton Trans., 2017,46, 6553-6569
Article type
Paper

Characterization and photocatalytic behavior of 2,9-di(aryl)-1,10-phenanthroline copper(I) complexes

M. M. Cetin, R. T. Hodson, C. R. Hart, D. B. Cordes, M. Findlater, D. J. Casadonte Jr., A. F. Cozzolino and M. F. Mayer, Dalton Trans., 2017, 46, 6553
DOI: 10.1039/C7DT00400A

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