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Shiraishi Y, Ishizumi K, Nishimura G, et al. Effects of metal cation coordination on fluorescence properties of a diethylenetriamine bearing two end pyrene fragments. J Phys Chem B. 2007;111(30):8812-22doi: 10.1021/jp072081s.
Shiraishi, Y., Ishizumi, K., Nishimura, G., & Hirai, T. (2007). Effects of metal cation coordination on fluorescence properties of a diethylenetriamine bearing two end pyrene fragments. The journal of physical chemistry. B, 111(30), 8812-22. https://doi.org/10.1021/jp072081s
Shiraishi, Yasuhiro, et al. "Effects of metal cation coordination on fluorescence properties of a diethylenetriamine bearing two end pyrene fragments." The journal of physical chemistry. B vol. 111,30 (2007): 8812-22. doi: https://doi.org/10.1021/jp072081s
Shiraishi Y, Ishizumi K, Nishimura G, Hirai T. Effects of metal cation coordination on fluorescence properties of a diethylenetriamine bearing two end pyrene fragments. J Phys Chem B. 2007 Aug 02;111(30):8812-22. doi: 10.1021/jp072081s. Epub 2007 Jun 29. PMID: 17602521.
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J Phys Chem B. 2007 Aug 02;111(30):8812-22. doi: 10.1021/jp072081s. Epub 2007 Jun 29.

Effects of metal cation coordination on fluorescence properties of a diethylenetriamine bearing two end pyrene fragments.

The journal of physical chemistry. B

Yasuhiro Shiraishi, Katsutake Ishizumi, Go Nishimura, Takayuki Hirai

Affiliations

  1. Research Center for Solar Energy Chemistry and Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, Toyonaka 560-8531, Japan. [email protected]

PMID: 17602521 DOI: 10.1021/jp072081s

Abstract

Fluorescence properties of a diethylenetriamine bearing two end pyrene fragments (L) have been studied in water, where effects of adding metal cations (Zn2+, Cd2+, Cu2+, Hg2+, Ag+) on the emission properties of L have been studied. Without metal cations, L shows dual-mode fluorescence consisting of monomer and excimer emissions. The monomer emission intensity (I(M)) is strong at acidic pH but decreases with a pH increase because of an electron transfer (ET) from the unprotonated nitrogen atoms to the excited pyrene fragment. The excimer emission is due to the static excimer formed via a direct photoexcitation of the intramolecular ground-state dimer (GSD) of the end pyrene fragments. The excimer emission intensity (I(E)) is weak at acidic pH but increases with a pH increase because of the GSD stability increase associated with the deprotonation of the polyamine chain. Addition of metal cations leads to I(M) decrease, where chelation-driven I(M) enhancement does not occur even with diamagnetic Zn2+ and Cd2+ at any pH. This is because a pyrene-metal cation pi-complex, formed via a donation of pi-electron of the pyrene fragment to the adjacent metal center, suppresses the monomer photoexcitation. I(E) also decreases upon addition of metal cations because the pyrene-metal cation pi-complex weakens pi-stacking interaction of the end pyrene fragments, leading to GSD stability decrease. The emission properties of L-Zn2+ complexes were studied by means of time-resolved fluorescence decay measurements, and the effects of adding a less-polar organic solvent were also studied to clarify the detailed emission properties.

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