Solid-state room-temperature phosphorescence activated by the end-capping strategy of cyano groups

Avoiding the tedious process of crystal cultivation and directly obtaining organic crystals with desirable phosphorescent performance is of great significance for studying their structure and properties.Herein,a set of benzophenone-cored phos-phors with bright green afterglow are obtained on a large scale through in-situ generation via an end-capping strategy to suppress non-radiative triplet excitons and reinforce the intermolecular interactions.The ordered arrangement of phosphors with alkyl-cyano groups as regulators is crucial for the enhancement of room-temperature phosphorescence(RTP)emission,which has been further verified by the attenuated lifetimes in isolated states through the formation of inclusion complexes upon binding with pillar[5]arenes.Moreover,the hierarchical interactions of phos-phors,including hydrogen bonding,π-πstacking interactions,and van der Waals forces,are quantified by crystal structures and theoretical calculation to deeply inter-pret the origins of RTP emission.With this study,we provide a potential strategy for the direct acquisition of crystalline organic phosphors and modulation of RTP.

Mechanistic Study on the Dominant Promotion Effect of Al-/Ti-/Zr-modifications over the VOx/SiO2 UHMWPE Catalysts

Recently, we reported the first VOx/SiO2 ethylene polymerization catalyst for making Cl-free UHMWPE, and found the dominant promotion effects of Al-/Ti-/Zr-modifications over this catalyst system(Macromol. Chem. Phys. 2017, 218, 1600443). In this work, density functional theory is applied to investigate the underlying mechanism of this remarkable promotion effect of Al-/Ti-/Zrmodifications on a molecular and atomic level. The cluster model with V(Ⅲ) is found to be the most possible active site due to its lowest overall energy barrier for monomer insertion, though the process of C2H4 coordination and the subsequent formation of transition state are most energy favored for V(Ⅱ) species. By modifying one of or both V―O―Si in the active model with V―O―M(M = Al, Ti, or Zr),the energy barrier for the binding of the upcoming C2H4 gets lower(particularly for Al-and Zr-modified catalysts), and the transition state also becomes more stable. Generally, the insertion process of C2H4 gets easier after support Al-/Ti-/Zr-modifications. This dominant promotion effect is partially ascribed to the more enriched positive charge distribution on or nearby the V center, and the narrower energy gap between the LUMO of model catalysts and the HOMO of C2H4 for these modified catalysts also contributes much. In addition, the decreased steric hindrance around the V center should be taken into account for the modified models as well. Furthermore, the Br?nsted acidity of the catalysts is investigated by introducing a pendent hydroxyl group to the model catalysts, which has a close contact with the V center. Similar promotion effect of support modification by Al, Ti, and Zr could still be observed.