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Mechanochemical reactions of benzene-1,4-dicarboxylate (BDC2−) and lanthanide carbonates, Ln2(CO3)3·xH2O (Ln = Sm, Eu, Gd, Tb) yield phase pure lanthanide coordination polymers, (Ln0.5Gd0.5)2(1,4-BDC)3(H2O)4 with Ln = Sm, Eu, Tb, which are isostructural with Tb2(1,4-BDC)3(H2O)4 as confirmed by powder X-ray diffraction and vibrational spectroscopy. Upon excitation with UV light all three compounds display strong emissions, characteristic for the respective optically active lanthanide ion, namely, red for Eu3+, green for Tb3+ and orange-red for Sm3+. In case of the Tb3+-containing compound, the energy difference between the triplet energy level of benzene-1,4-dicarboxylate ligand (BDC2−) allows for the most efficient BDC2−–Tb3+ energy transfer. As a consequence, an intense green luminescence with rather long lifetime (0.81 ms) and high quantum yield (22%) is observed after allowed excitation of the BDC2− ligand. The compounds are paramagnetic with no onset of long range magnetic ordering down to liquid He temperatures.

new journal of chemistry

Mechanochemical synthesis, luminescent and magnetic properties of lanthanide benzene-1,4-dicarboxylate coordination polymers (Ln0.5Gd0.5)2 (1,4-BDC)3(H2O)4; Ln = Sm, Eu, Tb