Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence

A new strategy for the easy polymerization of anionic [Ln(Q^cy)₄]^- (HQ^cy-4-(cyclohexanecarbonyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one) into two-dimensional layers of [AgLn(Q^cy)₄]_n (Ln = Sm, Eu, Gd, Tb and Dy) is proposed by binding the single molecular anions [Ln(Q^cy)₄]^- to silver cations through the coordination of the pyridinic nitrogen atoms of the pyrazolonate rings. The luminescent properties of [AgLn(Q^cy)₄]_n have been studied in detail, and it was shown that the previously described low photoluminescence quantum yield (PLQY) of [Eu(Q^cy)₄]^- is due to Ligand-To-Metal Charge Transfer (LMCT) quenching, which is effectively suppressed in the heterometallic [AgEu(Q^cy)₄]_n polymer. Sensibilization coefficients for H₃O[Eu(Q^cy)₄], [AgEu(Q^cy)₄]_n, and H₃O[Sm(Q^cy)₄] complexes (n ≈ 1) were estimated via theoretical analysis (also by using Judd-Ofelt theory for Sm³⁺) and PLQY measurements.