Three europium complexes with the terdentate N-donor ligand 2,6-bis(1H-pyrazol-3-yl)pyridine (L) have been synthesized, and their crystal structures have been determined. The ligand/metal ratios in these complexes are 3, 2, and 1. The photophysical properties of the complexes indicate more efficient ligand sensitization of europium emission for the homoleptic complex.
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Angew Chem Int Ed Engl
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Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211, Geneva 4, Switzerland.
To date, the piling up of successive photons of low energies (near infrared; NIR) using a single lanthanide center and linear optics to ultimately produce upconverted visible emission was restricted to low-phonon solid materials and nanoparticles. Now we show that the tight helical wrapping of three terdentate N-donor ligands around a single nine-coordinate trivalent erbium cation provides favorable conditions for a mononuclear molecular complex to exhibit unprecedented related upconverted emission. Low power NIR laser excitations into the metal-centered transitions Er( I ← I ) at 801 nm or Er( I ← I ) at 966 nm result in upconverted blue-green emissions, where two or three photons respectively are successively absorbed by a molecular lanthanide complex possessing high-energy vibrations.
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Inorg Chem
May 2018
Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094 , India.
A terdentate multiple N donor ligand, 2,6-bis(1 H-tetrazol-5-yl)pyridine (HBTzP), was synthesized, and its complexation with trivalent americium, neodymium, and europium was studied using single-crystal X-ray diffraction, attenuated total reflectance-fourrier transform infrared spectroscopy, time-resolved fluorescence spectroscopy, UV-vis absorption spectrophotometry. Higher complexation strength of BTzP toward trivalent actinide over lanthanides as observed from UV-vis spectrophotometric study resulted in an effective separation of Am and Eu in liquid-liquid extraction studies employing N,N, N',N'-tetra- n-octyl diglycolamide in the presence of BTzP as the aqueous complexant. The selectivity of BTzP toward Am over Eu was further investigated by DFT computations, which indicated higher metal-ligand overlap in the Am complex as indicated from the metal-nitrogen bond order and frontier molecular orbital analysis of the BTzP complexes of Am and Eu.
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Dalton Trans
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Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400085, India.
A systematic study on the Ln(3+) complexation behaviour with two terdentate 'N' donor ligands of varying structural rigidity, viz. 5,6-dimethyl-(1,2,4)-triazinylbipyridine (Me2TBipy) and 5,6-dimethyl-(1,2,4)-triazinylphenanthroline (Me2TPhen), is performed in the present work by UV-Vis spectrophotometry, time resolved fluorescence spectroscopy (TRFS) and electrospray ionization mass spectrometric (ESI-MS) studies. These studies indicate the formation of a 1 : 1 complex of La(3+), 1 : 2 complexes of Eu(3+) and Er(3+) with both the ligands.
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URCHEMS, Université Constantine 1 (ex. Mentouri), route de Ain El Bey, 25017 Constantine, Algeria.
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Department of Applied Biology & Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, People's Republic of China.
Three europium complexes with the terdentate N-donor ligand 2,6-bis(1H-pyrazol-3-yl)pyridine (L) have been synthesized, and their crystal structures have been determined. The ligand/metal ratios in these complexes are 3, 2, and 1. The photophysical properties of the complexes indicate more efficient ligand sensitization of europium emission for the homoleptic complex.
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