25902-98-1Relevant academic research and scientific papers
Understanding Intrinsic Light Absorption Properties of UiO-66 Frameworks: A Combined Theoretical and Experimental Study
Hendrickx, Kevin,Vanpoucke, Danny E. P.,Leus, Karen,Lejaeghere, Kurt,Van Yperen-De Deyne, Andy,Van Speybroeck, Veronique,Van Der Voort, Pascal,Hemelsoet, Karen
, p. 10701 - 10710 (2015)
A combined theoretical and experimental study is performed in order to elucidate the effects of linker functional groups on the photoabsorption properties of UiO-66-X materials. This study, in which both mono- and difunctionalized linkers (with X = OH, NH2, or SH) are investigated, aims to obtain a more complete picture of the choice of functionalization. Static time-dependent density functional theory calculations combined with molecular dynamics simulations are performed on the linkers, and the results are compared to experimental UV/vis spectra in order to understand the electronic effects governing the absorption spectra. The disubstituted linkers show larger shifts than the monosubstituted variants, making them promising candidates for further study as photocatalysts. Next, the interaction between the linker and the inorganic part of the framework is theoretically investigated using a cluster model. The proposed ligand-to-metal-charge transfer is theoretically observed and is influenced by the differences in functionalization. Finally, the computed electronic properties of the periodic UiO-66 materials reveal that the band gap can be altered by linker functionalization and ranges from 4.0 down to 2.2 eV. Study of the periodic density of states allows the band gap modulations of the framework to be explained in terms of a functionalization-induced band in the band gap of the original UiO-66 host.
On-Demand Cyclophanes: Substituent-Directed Self-Assembling, Folding, and Binding
Skowron, Pierre-Thomas,Dumartin, Melissa,Jeamet, Emeric,Perret, Florent,Gourlaouen, Christophe,Baudouin, Anne,Fenet, Bernard,Naubron, Jean-Valère,Fotiadu, Frédéric,Vial, Laurent,Leclaire, Julien
, p. 654 - 661 (2016/01/25)
A family of p-cyclophanes based on bis- or tetrafunctionalized 1,4-bisthiophenol units linked by disulfide bridges was obtained by self-assembly on a gram scale and without any chromatographic purification. The nature of the functionalities borne by these so-called dyn[4]arenes plays a crucial role on their structural features as well as their molecular recognition abilities. Tuning these functions on demand yields tailored receptors for cations, anions, or zwitterions in organic or aqueous media.
