Crystallochemiluminescence accompanying the fluorination of europium (III) nitrate by xenon difluoride in acetonitrile solution

Add time:07/18/2019    Source:sciencedirect.com

Crystallochemiluminescence (CCL) has been discovered in the fluorination of Eu(NO3)3•6H2O with xenon difluoride in acetonitrile. It has been found that the following electron-excited particles act as CCL emitters: elemental xenon *Xe (λem = 458 nm), xenon in an intermediate (+1) oxidation state *Xe+ (λem = 416, 484, 542 nm), europium ion *Eu(III) (λem = 610 nm), and singlet oxygen 1O2 (λem = 1270 nm). A mechanism has been suggested for the formation of electron-excited intermediates and products of XeF2 catalytic decomposition on crystalline juvenile surface of EuF3•nH2O during its crystallization in acetonitrile. The heats of the assumed stages have been estimated in CCSD(T)/QZP approximation. It has been shown that the chain of reactions resulting in intermediates of XeF2 decomposition, including excited states, begins with the high-energy reaction of XeF2 with Eu(III) (ΔH / ΔG = 881 / 910 kJ/mol). The reaction in question is a rare example of a multi-emitter process that produces a number of electron-excited products: *Xe, *Xe+, *Eu(III), and singlet oxygen 1O2.

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