Journal
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
Volume 358, Issue -, Pages 147-156Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jphotochem.2018.02.015
Keywords
Rhenium complex; Photochemistry; Excited states; Pterin; TD-DFT
Categories
Funding
- CONICET [PIP 0389, PIP 112-2013-01-00236CO]
- ANPCyT [PICT 2012-0423, PICT 2015-0374]
- UNLP of Argentina [11X/611, 11/X679]
- CONICET
- Division of Chemical Sciences, Geosciences and Biosciences, Basic Energy Sciences, Office of Science, United States Department of Energy [DE-FC02-04ER15533]
Ask authors/readers for more resources
In this work, we present a whole and deep study on the thermal redox and the photophysical and photochemical reactions of a tricarbonyl Re(I) complex coordinating Pterin, fac-Re-l(CO)(3)(pterin)(H2O) (pterin = 2-amino-4-oxo-3H-pteridine). In aqueous solutions, the fluorescence of the complex is attributed to the emitting (IL)-I-1 state (tau(emi); similar to 7.6 ns). In MeCN, however, the luminescence was ascribed to an overlapping dual emission from (IL)-I-1 and (MLCT)-M-3 states (tau(emi1) = 8.0 ns and tau(emi2) = 1.0 mu s). Oxygen quenching of the (MLCT)-M-3 based luminescence occurred with k(q) =1.6 x 10(9) M-1 s(-1). In glasses at 77 K, nevertheless, the (MLCT)-M-3 prevailed over (IL)-I-1. states. Flash photolysis experiments in aqueous solutions showed the spectrum of (IL)-I-3 while in MeCN the presence of (MLCT)-M-3 was evident. Pulse radiolysis experiments under oxidizing and reducing environments were performed in aqueous solutions of the Re-Pterin complex. By performing multivariate curve resolution - alternating least-squares (MCR-ALS), two species were identified under reducing conditions: an intermediate related to the semireduced radical of pterin ligand and the dihydrogenated [Re(CO)(3)(7,8-PtrH(2))(H2O)] product. TD-DFT calculations helped to ascertain the nature of these species. Flash photolysis experiments where the excited states were reduced with triethylamine were in good agreement with pulse radiolysis experiments under reductive conditions. The oxidized transient spectrum was also obtained by pulse radiolysis, which compares very well with those published for Re(II) species, leading us to propose oxidation in the metal core as the reaction product of the transient under oxidizing conditions. The combination of different spectroscopic techniques along with the theoretical calculation allowed elucidating the nature, dynamics and reactivity of the excited states prevail in a Re-Pterin complex. This is of the particular importance considering that equivalent studies have not been reported for any other rhenium complex of substituted pterins nor for complexes of other transition metal ions of pterin derivatives. (C) 2018 Elsevier B.V. All rights reserved.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available