Two discrete mononuclear complexes, [Tb(bbpen)(NO3)] (I) and [Tb(bbppn)(NO3)] (II), for which H2bbpen = N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine and H2bbppn = N,N′-bis(2-hydroxylbenzyl)-N,N'-bis(pyridin-2-ylmethyl)-1,2-propanediamine, were synthesized and characterized by FTIR, Raman, and photoluminescence (PL, steady-state and time-resolved modes) spectroscopy. The attachment of a methyl group to the ethylenediamine portion of the ligand backbone differentiates II from I and acts as a determining feature to both the structural and optical properties of the former. The single-crystal X-ray structure of H2bbppn is described here for the first time, while that of complex II has been redetermined in the monoclinic C2 space group in light of new diffraction data. In II, selective crystallization leads to spontaneous resolution of enantiomeric molecules in different crystals. Absolute emission quantum yields (φ) and luminescence excited-state lifetimes (at room temperature and 11 K) were measured for both complexes. Despite their similar molecular structures, I and II exhibit remarkably different φ values of 21 ± 2% and 67 ± 7%, respectively, under UV excitation at room temperature. Results of quantum-mechanical (DFT and TD-DFT) calculations and experimental PL measurements also performed for H2bbpen and H2bbppn confirmed that both ligands are suitable to work as "antennas" for TbIII. Considering the 5D4 lifetime profiles and the significantly higher absolute quantum yield of II, it appears that thermally active nonradiative pathways present in I are minimized in II due to differences in the conformation of the ethylenediamine bridge.
Promoting a Significant Increase in the Photoluminescence Quantum Yield of Terbium(III) Complexes by Ligand Modification / Gregorio T.; Leao J.D.M.; Barbosa G.A.; Ramos J.D.L.; Om Kumar Giese S.; Briganti M.; Rodrigues P.C.; De Sa E.L.; Viana E.R.; Hughes D.L.; Carlos L.D.; Ferreira R.A.S.; Macedo A.G.; Nunes G.G.; Soares J.F.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 58:(2019), pp. 12099-12111. [10.1021/acs.inorgchem.9b01397]
Promoting a Significant Increase in the Photoluminescence Quantum Yield of Terbium(III) Complexes by Ligand Modification
Briganti M.;
2019
Abstract
Two discrete mononuclear complexes, [Tb(bbpen)(NO3)] (I) and [Tb(bbppn)(NO3)] (II), for which H2bbpen = N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine and H2bbppn = N,N′-bis(2-hydroxylbenzyl)-N,N'-bis(pyridin-2-ylmethyl)-1,2-propanediamine, were synthesized and characterized by FTIR, Raman, and photoluminescence (PL, steady-state and time-resolved modes) spectroscopy. The attachment of a methyl group to the ethylenediamine portion of the ligand backbone differentiates II from I and acts as a determining feature to both the structural and optical properties of the former. The single-crystal X-ray structure of H2bbppn is described here for the first time, while that of complex II has been redetermined in the monoclinic C2 space group in light of new diffraction data. In II, selective crystallization leads to spontaneous resolution of enantiomeric molecules in different crystals. Absolute emission quantum yields (φ) and luminescence excited-state lifetimes (at room temperature and 11 K) were measured for both complexes. Despite their similar molecular structures, I and II exhibit remarkably different φ values of 21 ± 2% and 67 ± 7%, respectively, under UV excitation at room temperature. Results of quantum-mechanical (DFT and TD-DFT) calculations and experimental PL measurements also performed for H2bbpen and H2bbppn confirmed that both ligands are suitable to work as "antennas" for TbIII. Considering the 5D4 lifetime profiles and the significantly higher absolute quantum yield of II, it appears that thermally active nonradiative pathways present in I are minimized in II due to differences in the conformation of the ethylenediamine bridge.File | Dimensione | Formato | |
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