Luminescence of Inorganic Nitrite Salts

Abstract

Nitrite salts of the post-transition-series metals exhibit a long-lived luminescence centered at ∼5500 Å. This emission is characteristic of both the solid state and frozen glassy solutions. It is suggested that this emission originates in a triplet state (T1) of the system, and that, in fact, it is a phosphorescence of T1→S0 molecular type connecting with the ground singlet state (S0). It is shown that the spin–orbit coupling responsible for the enhanced intersystem crossing is introduced by the metal counterion and that such introduction is also dependent on the presence of nitrite-counterion covalency. The increased spin–orbit coupling is manifested in the following ways: (i) a decrease in the phosphorescence lifetime, τp, (ii) an increase in the relative quantum yield ratio Φp / Φf of phosphorescence to fluorescence, (iii) an increase in the T1←S0 absorptivity—which absorptivity is responsible for the yellow-orange colors of the heavy-metal nitrites.