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Wavelength-Dependent Singlet Oxygen Generation in Luminescent Lanthanide Complexes with a Pyridine-Bis(Carboxamide)-Terthiophene Sensitizer.

Authors:
Katherine R Johnson Sebastian B Vittardi Manuel A Gracia-Nava Jeffrey J Rack Ana de Bettencourt-Dias

Chemistry 2020 Jun 19;26(32):7274-7280. Epub 2020 May 19.

Department of Chemistry, University of Nevada, Reno, Reno, NV, 89557, USA.

Lanthanide ion (Ln ) complexes, [Ln(3Tcbx) ] (Ln =Yb , Nd , Er ) are isolated with a new pyridine-bis(carboxamide)-based ligand with a 2,2':5',2''-terthiophene pendant (3TCbx), and their resulting photophysical properties are explored. Upon excitation of the complexes at 490 nm, only Ln emission is observed with efficiencies of 0.29 % at 976 nm for Ln =Yb and 0.16 % at 1053 nm for Ln =Nd . Er emission is observed but weak. Upon excitation at 400 nm, concurrent O formation is seen, with efficiencies of 11 % for the Yb and Nd complexes and 13 % for the Er complex. Owing to the concurrent generation of O , as expected, the efficiency of metal-centered emission decreases to 0.02 % for Yb and 0.05 % for Nd . The ability to control O generation through the excitation wavelength indicates that the incorporation of 2,2':5',2''-terthiophene results in access to multiple sensitization pathways. These energy pathways are unraveled through transient absorption spectroscopy.

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http://dx.doi.org/10.1002/chem.202000587DOI Listing
June 2020

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