A comparative spectroscopic study of U(III)/Am(III) and Ln(III) complexed with N-donor ligands

A TRLFS Study on the Complexation of CmIII and EuIII with 2,6‐Bis(5,6‐dipropyl‐1,2,4‐triazin‐3‐yl)pyridine in Water/Methanol Mixture

“…Thus we conclude the complex to be of the same composition as the complex which forms in 1-octanol. [16,17] As was shown for BTBP ligands, [23] the number of coordinated quenching molecules for Cm III cannot be calculated according to Equation (4) since additional quenching processes by intramolecular energy transfer between the Cm III ion and the organic ligand occur. The same applies to the BTP ligands.…”

“…However, the fluorescence lifetime is in good agreement with that of the [Cm(nPr-BTP) 3 ] 3+ complex in 1-octanol. [17] Species 1 cannot be characterised in detail due to its low concentration. However, from a previous work [17] it is deduced from the position and shape of its emission spectrum to represent a 1:1 species.…”

“…Figure 6 shows the double logarithmic plot of the spectroscopically determined concentration ratios of the different species in solution at The fluorescence spectra of both 1:3 complex species are identical to the spectra of the [M(nPr-BTP) 3 ] 3+ complexes which form in 1-octanol. [16,17] However, the present study is performed in a mixture of water and methanol so that inner sphere hydration has to be considered. To demonstrate the absence of solvent molecules in the first coordination sphere the fluorescence lifetimes of both 1:3 complexes is determined.…”

“…[15][16][17] To confirm the formation of a metal ion:ligand 1:3 species upon addition of nPr-BTP to the solvated metal ions ([M(solv.)] 3+ ), slope analysis of the obtained titration results is performed using the following Equation (1): (1) It follows Equation (2): (2) According to this, a linear correlation between the logarithm of the concentration ratio…”

Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide and Lanthanoid-Actinide Complexes Possessing Redox-Active Bridging Ligands

“…With substantial extension of 5f-orbitals from the core, early actinide compounds (Th-Pu) have shown signatures of significant covalent metal-ligand bonding, giving rise to unique chemical and physicochemical properties. [1][2][3][4][5][6][7][8] The introduction of multiple metal ions into structural frameworks known to exhibit f-element metal-ligand covalency creates the possibility for metal-metal electronic delocalization and mixed-valency. The ability of f-element materials to form mixed-valent species has direct consequences on their corrosion, speciation, and environmental chemistry.…”