Infrared 4f-Luminescence of Erbium(III) Complexes with Tetrapyrrole Ligands

Nikolay N. Semenishyn,^a Sergii S. Smola,^a Natalya V. Rusakova,^a^@ Alexander G. Martynov,^b Kirill P. Birin,^b Yulia G. Gorbunova,^b,c and Aslan Yu. Tsivadze^b,c

^aA.V. Bogatsky Physico-Chemical Institute, 65080 Odessa, Ukraine

^bA.N. Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, 119071 Moscow, Russia

^cN.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991 Moscow, Russia

^@Corresponding author E-mail: natalirusa@yandex.ua

DOI: 10.6060/mhc180691r
Macroheterocycles 2018 11(3) 262-268

The luminescent properties of the series of erbium(III) complexes of various coordination types with different tetrapyrrole macrocycles (porphyrins, phthalocyanines and corroles) are discussed in this paper. The investigated series of compounds include mononuclear porphyrinato complexes (metal-ligand ratio 1:1, tppEr(acac)), sandwich phthalocyaninato-porphyrinato type complexes (metal-ligand ratio 1:2 [(15C5)₄Pc]Er[(4-BrC₆H₄)₄Por] or 2:3 – (Pc)Er[(15C5)₄Pc]Er(Pc) and [(15C5)₄Pc]Er[(15C5)₄Pc]Er(Pc)), ditopic porphyrins and corroles possessing peripheral lanthanides binding (metal-ligand ratio 1:1, Er-edta-H₂atpp·2H₂O, Er-Hdtpa-H₂atpp, Er-edta-H₃dpfc·2H₂O andEr-Hdtpa-H₃dpfc). 4f-Luminescence in the near-infrared region is observed in all studied Er-complexes as a result of intramolecular transfer of excitation energy. The unique features of each type of complexes are discussed in details. The peripheral complexes are dual-emissive: they display both erbium(III) 4f-emission in near-infrared and molecular fluorescence in the visible spectral region. The values of quantum yield of molecular fluorescence as well as the intensity of 4f-luminescence are estimated. It was found that the binding type of erbium(III) plays a key role in the macrocycle excited state relaxation. The double-decker heteroleptic complex [(15C5)₄Pc]Er[(4-BrPh)₄Por] possesses unusual emission behaviour.

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Infrared 4f-Luminescence of Erbium(III) Complexes with Tetrapyrrole Ligands

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