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International Journal of Photoenergy
Volume 3, Issue 3, Pages 143-164

Light driven isomerization of coordinated ligand and modulation of fac-[Re(CO)3(phen)(trans-bpe)]PF6 photoluminescence in rigid media

Instituto de Química, Universidade de São Paulo - Av. Lineu Prestes, 748, São Paulo , SP 05508-900, Brazil

Copyright © 2001 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


The excited state reactivity and photophysical properties of fac-[Re(CO)3(phen)(L)]PF6 (phen = 1,10-phenanthroline, L = trans- or cis-1,2-bis(4-pyridyl)ethylene, bpe) in PMMA (poly(methyl methacrylate)) films have been investigated and compared with those in acetonitrile solution.

313 or 365 nm irradiation of the rhenium complex in PMMA leads to UV-vis spectral changes due to the transcis isomerization of the coordinated bpe ligand. The fac-[Re(CO)3(phen)(cis-bpe)]+ product presents a markedly enhanced luminescence due to a lower lying metal-to-ligand charge transfer (MLCT) excited state in the cis isomer. This emitting property can be conveniently applied as a probe or sensor.

The cis is omer ratio in the photostationary state (PSS) is substantially smaller in solid films than in solution. The photochemical behavior of the free trans-1,2-bis(4-pyridyl)ethylene in PMMA is also reported to establish comparisons with the investigation carried out in acetonitrile solution as well as with the behavior of the coordinated ligand.