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Photoisomerization of di-nuclear rhenium(i) bpe-based compounds

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Abstract

Di-nuclear [{(NN)(CO)3Re}2(trans-bpe)](PF6)2 complexes, NN = 4,7-diphenyl-1,10-phenanthroline (ph2phen) or 4,7-dichloro-1,10-phenanthroline (Cl2phen) and trans-bpe = trans-1,2-bis(4-pyridyl)ethylene, were synthesized and characterized by 1H NMR and UV-visible spectroscopy. Irradiation of acetonitrile solutions led to 1H NMR and UV-visible spectral changes ascribed to trans-to-cis photoisomerization processes showing that the presence of another Re(i)-moiety does not preclude the photoisomerization process. Quantum yields for the di-nuclear isomerization of [{(ph2phen)(CO)3Re}2(trans-bpe)]2+ were higher than those for the corresponding mono-nuclear compound process. Additionally, the higher quantum yield obtained with 254 nm irradiation for [{(Cl2phen)(CO)3Re}2(trans-bpe)]2+ showed, for the first time, that the singlet pathway could also be accessed in addition to the usually observed triplet one. The luminescence in fluid solution observed for the [{(NN)(CO)3Re}2(cis-bpe)]2+ complexes is able to efficiently photosensitize the generation of singlet O2.

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Acknowledgments

The authors would like to acknowledge financial support from the Brazilian agencies Fundação de Amparo a Pesquisa do Estado de São Paulo (FAPESP/Grant 2016/21993-6, 2017/07289-7, 2017/18063-0) and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq/Grant 454971/2014-1), and the Multiuser Central Facilities and Complexo Laboratorial Nanotecnológico (CLN) at UFABC and the Laboratory of Photochemical and Energy Conversion at Instituto de Química USP for experimental support.

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  1. Federal University of ABC–UFABC, Av. dos Estados 5001, Santo Andre, SP, 09210-170, Brazil

    Karina P. Morelli Frin, Denis C. da Rocha, Júlia F. Mamud & André S. Polo

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  1. Karina P. Morelli Frin
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  2. Denis C. da Rocha
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Correspondence to Karina P. Morelli Frin.

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Morelli Frin, K.P., da Rocha, D.C., Mamud, J.F. et al. Photoisomerization of di-nuclear rhenium(i) bpe-based compounds. Photochem Photobiol Sci 17, 1443–1449 (2018). https://doi.org/10.1039/c8pp00274f

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