Preparation, Structure and Spectroscopic Properties of NH 4 [Ln(S 2 CNH 2 ) 4 ] ⋅ H 2 O (Ln=La, Eu)

The title compounds were prepared under mild ambient conditions by a facile co-precipitation route. NH4[Eu(S2CNH2)4] ⋅ H2O (a) and NH4[La(S2CNH2)4] ⋅ H2O (b) crystallize isotypically in the monoclinic space group P21/c with a=8.4461(3), b=13.6367(3), c=16.2945(5) Å, β=103.759(2)° (for (a)), and a=8.50484(9), b=13.84476(16), c=16.20816(17) Å, β=103.7644(11)° for (b), respectively. The spectroscopic data reveal the presence of a ligand-to-metal charge transfer (LMCT) process of low energy in a and in the solid solutions NH4[La1−xEux(S2CNH2)4] ⋅ H2O (x=0.016 and 0.05). Despite of the consequent efficient luminescent quenching, it was possible to recorded excitation and emission spectra at room temperature. These spectra are characterized by narrow bands due to intraconfigurational-4f transitions of the Eu3+ ion. However, broad bands associated to the LMCT state were also observed, mainly for the solid solutions NH4[La1−xEux(S2CNH2)4] ⋅ H2O (x=0.016 and 0.05). Consequently, an intramolecular energy transfer mechanism is proposed, taking into account the role of the LMCT on the spectroscopic properties of dithiocarbamate complexes.


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