Energy transfer in coumarin-sensitised lanthanide luminescence: investigation of the nature of the sensitiser and its distance to the lanthanide ion

Abstract

A series of lanthanide complexes [Ln(dpxCy)₃]³⁻ have been synthesised. The ligands are composed of a coordinating dipicolinic acid backbone decorated with a polyoxyethylene arm fitted with a coumarin moiety at its extremity. The nature of the coumarin as well as the length of the linker have been varied. Upon excitation at 320 nm, the coumarin exclusively acts as an antenna while the dipicolinic acid core is not excited. Upon excitation below 300 nm, both parts are excited. With europium as a metal centre, the relaxation of the europium ion (intrinsic quantum yield Φ^Eu_Eu and radiative lifetime τ_r) is constant for all the studied ligands. Therefore, the observed differences in overall quantum yield (Φ^Eu_L) in such systems come exclusively from the variation of the terminal coumarin. The overall quantum yields of the studied complexes are low (Φ^Eu_L < 2% in aqueous solution). In order to rationalise the mechanism of the energy transfer and to improve the sensitisation efficiency (η_sens), the distance between the coumarin sensitiser and the lanthanide centre was explored in solution and compared to the solid state. In the solid state, a dramatic effect was confirmed, with an improvement of 80% in the quantum yield Φ^Eu_L for short linkers ((–CH₂CH₂O–)_n with n = 1 compared to n = 3). By monitoring the lifetime decay of the excited state of the lanthanide cation with nanosecond vs. microsecond time-resolved spectroscopy at low temperature, the sensitisation of the lanthanide ions by coumarin derivatives was demonstrated to mainly occur through the singlet excited state of the coumarin and not via the usual triplet pathway. No evidence of a different behaviour at room temperature was found by transient triplet–triplet absorption spectroscopy.