Sensing mechanism elucidation of a europium(III) metal–organic framework selective to aniline: A theoretical insight by means of multiconfigurational calculations

A theoretical procedure, via quantum chemical computations, to elucidate the detection principle of the turn-off luminescence mechanism of an Eu-based Metal-Organic Framework sensor (Eu-MOF) selective to aniline, is accomplished. The energy transfer channels that take place in the Eu-MOF, as well as understanding the luminescence quenching by aniline, were investigated using the well-known and accurate multiconfigurational ab initio methods along with sTD-DFT. Based on multireference calculations, the sensitization pathway from the ligand (antenna) to the lanthanide was assessed in detail, that is, intersystem crossing (ISC) from the S₁ to the T₁ state of the ligand, with subsequent energy transfer to the ⁵D₀ state of Eu³⁺. Finally, emission from the ⁵D₀ state to the ⁷F_J state is clearly evidenced. Otherwise, the interaction of Eu-MOF with aniline produces a mixture of the electronic states of both systems, where molecular orbitals on aniline now appear in the active space. Consequently, a stabilization of the T₁ state of the antenna is observed, blocking the energy transfer to the ⁵D₀ state of Eu³⁺, leading to a non-emissive deactivation. Finally, in this paper, it was demonstrated that the host-guest interactions, which are not taken frequently into account by previous reports, and the employment of high-level theoretical approaches are imperative to raise new concepts that explain the sensing mechanism associated to chemical sensors.