Synthesis, structure, and physico-optical properties of manganate(II)-based ionic liquids

Several ionic liquids (ILs) based on complex manganate(II) anions with chloro, bromo, and bis(trifluoromethanesulfonyl)amido (Tf(2)N) ligands have been synthesized. As counterions, n-alkyl-methylimidazolium (C(n)mim) cations of different chain length (alkyl=ethyl (C(2)), propyl (C(3)), butyl (C(4)), hexyl (C(6))) were chosen. Except for the 1-hexyl-3-methylimidazolium ILs, all of the prepared compounds could be obtained in a crystalline state at room temperature. However, each of the compounds displayed a strong tendency to form a supercooled liquid. Generally, solidification via a glass transition took place below -40 degrees C. Consequently, all of these compounds can be regarded as ionic liquids. Depending on the local coordination environment of Mn(2+), green (tetrahedrally coordinated Mn(2+)) or red (octahedrally coordinated Mn(2+)) luminescence emission from the (4)T(G) level is observed. The local coordination of the luminescent Mn(2+) centre has been unequivocally established by UV/Vis as well as Raman and IR vibrational spectroscopies. Emission decay times measured at room temperature in the solid state (crystalline or powder) were generally a few ms, although, depending on the ligand, values of up to 25 ms were obtained. For the bromo compounds, the luminescence decay times proved to be almost independent of the physical state and the temperature. However, for the chloro- and bis(trifluoromethanesulfonyl)amido ILs, the emission decay times were found to be dependent on the temperature even in the solid state, indicating that the measured values are strongly influenced by nuclear motion and the vibration of the atoms. In the liquid state, the luminescence of tetrahedrally coordinated Mn(2+) could only be observed when the tetrachloromanganate ILs were diluted with the respective halide ILs. However, for [C(3)mim][Mn(Tf(2)N)(3)], in which Mn(2+) is in an octahedral coordination environment, a weak red emission from the pure compound was found even in the liquid state at elevated temperatures.