Structure-Dependent Photoluminescence of Europium(III) Coordination Oligomeric Silsesquioxane: Synthesis and Mechanism

[Image: see text] The coordination environment of Eu(3+) is a crucial factor in the optical performance of the complex. Herein, a new kind of oligomeric silsesquioxane was employed to improve the coordination environment of central ions, the luminescence intensity of which was greatly enhanced with an efficient emission peak at 619 nm. More importantly, the photoluminescent properties of the product will be altered because of the formation of the Si–O–Si structure. The relevant mechanism has also been investigated and proposed by a series of characterization analyses. Additionally, the fluorescence lifetime, intrinsic quantum yield, and energy transfer efficiency were calculated. In addition, the observed trend of Judd–Ofelt intensity parameters was used to justify the coordination environment of Eu(3+) ions. The experimental results reveal that the sol–gel reaction of the ligands can effectively promote intramolecular energy transfer. In addition, we introduced four theory modules of ligands (LSi, LSi-1, LSi-2, and LSi-3) with certain rules of formation of Si–O–Si, and density functional theory (DFT) and time-dependent DFT (TD-DFT) were used to explore their excited electron transfer process and their electronic absorption spectra, combined with Marcus theory. The calculated results show that the sol–gel reaction will induce the separation of the distribution of excited holes and electrons, leading to an efficient charge-transfer (CT) process. The predictable results were in good accordance with the experimental findings. Consequently, the sol–gel reaction occurring among ligands will be attributed to an efficient CT process, leading to a strong luminescence intensity, as observed experimentally.