Abstract
The synthesis, characterization, photophysical properties, theoretical calculations, and catalytic studies 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.
Original language | English |
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Pages (from-to) | 6553-6569 |
Number of pages | 17 |
Journal | Dalton Transactions |
Volume | 46 |
Issue number | 20 |
Early online date | 12 Apr 2017 |
DOIs | |
Publication status | Published - 28 May 2017 |
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Characterization and photocatalytic behavior of 2,9-di(aryl)-1,10-phenanthroline copper(I) complexes (dataset)
Cetin, M. M. (Creator), Hodson, R. T. (Creator), Hart, C. R. (Creator), Cordes, D. B. (Creator), Findlater, M. (Creator), Casadonte, Jr., D. J. C. J. (Creator), Cozzolino, A. F. (Creator) & Mayer, M. F. (Creator), Cambridge Crystallographic Data Centre, 2017
https://dx.doi.org/10.5517/ccdc.csd.cc123hm9 and 3 more links, https://dx.doi.org/10.5517/ccdc.csd.cc123hnb, https://dx.doi.org/10.5517/ccdc.csd.cc123hpc, https://dx.doi.org/10.5517/ccdc.csd.cc123hqd (show fewer)
Dataset