Dalian University of Technology

About: Dalian University of Technology is a education organization based out in Dalian, China. It is known for research contribution in the topics: Catalysis & Finite element method. The organization has 60890 authors who have published 71921 publications receiving 1188356 citations. The organization is also known as: Dàlián Lǐgōng Dàxué.

Tuning the luminescence lifetimes of ruthenium(II) polypyridine complexes and its application in luminescent oxygen sensing

Abstract: Ru(Phen)(bpy)2 (1) and its new derivatives (2–5) with pyrenyl or ethynylated pyrene and phenyl units appended to the 3-position of the phenanthroline (Phen) ligand were prepared and these complexes generate long-lived room temperature phosphorescence in the red and near IR range (600–800 nm). The photophysical properties of these complexes were investigated by UV-Vis absorption, luminescence emission, transient absorption spectra and DFT/TDDFT calculations. We found the luminescence lifetime (τ)can be drastically extended by ligand modification (increased up to 140-fold), e.g. τ = 58.4 μs for complex 3 (with pyrenyl ethynylene appendents) was found, compared to τ = 0.4 μs for the reference complex 1. Ethynylated phenyl appendents alter the τ also (complex 2, τ = 2.4 μs). With pyrenyl appendents (4 and 5), lifetimes of 2.5 μs and 9.2 μs were observed. We proposed three different mechanisms for the lifetime extension of 2, 3, 4 and 5. For 2, the stabilization of the 3MLCT state by π-conjugation is responsible for the extension of the lifetime. For 3, the emissive state was assigned as an intra-ligand (IL) long-lived 3π–π* state (3IL/3LLCT, intraligand or ligand-to-ligand charge transfer), whereas a C–C single bond linker results in a triplet state equilibrium between 3MLCT state and the pyrene localized 3π–π* triplet state (3IL, e.g.4 and 5). DFT/TDDFT calculations support the assignment of the emissive states. The effects of the lifetime extension on the oxygen sensing properties of these complexes were studied in both solution and polymer films. With tuning the emissive states, and thus extension of the luminescence lifetimes, the luminescent O2 sensing sensitivity of the complexes can be improved by ca. 77-fold in solution (I0/I100 = 1438 for complex 3, vs. I0/I100 = 18.5 for complex 1). In IMPES-C polymer films, the apparent quenching constant KSVapp is improved by 150-fold from 0.0023 Torr−1 (complex 1) to 0.35 Torr−1 (complex 3). The KSVapp value of complex 3 is even higher than that of PtOEP under similar conditions (0.15 Torr−1).

Solvothermal synthesis of NH2-MIL-125(Ti) from circular plate to octahedron

Abstract: The MOF material NH2-MIL-125(Ti) was synthesized through the solvothermal method, and the morphology can be controlled by simply modulating the concentration of the reactants during crystallization, which ranges from circular plate through tetragon to octahedron All samples were characterized by SEM, XRD, FT-IR, UV Raman spectra, TGA, Ar adsorption/desorption and UV-vis spectra In situ XRD results show that this Ti-incorporated MOF is highly thermostable until 290 °C It is interesting to find that the light response of NH2-MIL-125(Ti) crystals is closely related to their morphology, and the absorption edges of different morphologies range from 480 nm to 533 nm with band gaps of 26 to 23 eV, making them potential candidates for photocatalytic applications