202865-84-7Relevant articles and documents
Synthesis and Properties of Rhomboidal Macrocyclic Subunits of Graphdiyne-Like Nanoribbons
Desroches, Maude,Courtemanche, Marc-André,Rioux, Geneviève,Morin, Jean-Fran?ois
, p. 10634 - 10642 (2015)
Rhomboidal macrocyclic subunits of graphdiyne-like nanoribbon (GDNR) bearing both alkyne and diyne units, allowing for multichannel π-conjugation, were synthesized using an oxidative Glaser-type ring closing reaction. These subunits, called the "meshes" of the nanoribbon, possess phenyl groups with decyloxy solubilizing chains on each corner. The yields of the ring closing reaction highly depend on the metal (Cu or Pd) catalyst used for the macrocyclization step. Increasing the width of the meshes from one macrocycle to two fused macrocycles resulted in a decrease of the bandgap by 0.23 eV as shown by optical spectroscopy. The optimized geometries of the meshes alongside their HOMO and LUMO orbitals were calculated using DFT calculations at the B3LYP/6-31+G? level of theory. The results showed a nearly planar conformation for both meshes with HOMO and LUMO orbitals entirely delocalized over the molecules.
Heterohelicenes with embedded P-chiral 1H-phosphindole or dibenzophosphole units: Diastereoselective photochemical synthesis and structural characterization
Yavari, Keihann,Retailleau, Pascal,Voituriez, Arnaud,Marinetti, Angela
supporting information, p. 9939 - 9947 (2013/08/23)
The oxidative photocyclization reactions of olefins that contain 1H-phosphindole or dibenzophosphole substituents have been applied to the synthesis of P/N-bi-heterosubstituted dimeric helicenes, as well as of new [6]- and [8]phosphahelicenes. In these photocyclization processes, the configuration of the stereogenic phosphorus center dictates the sense of helical chirality. Thus, by starting from enantiomerically pure P-menthylphosphole-oxide units, this method affords enantiopure helical compounds. The helical phosphine oxides were characterized by X-ray diffraction. After reduction of the phosphine-oxides, the corresponding helical phosphines have been used as ligands in transition-metal complexes. The X-ray crystal structure of a gold chloride complex of a [6]helicene is reported. From phosphindoles to helicenes: Olefins with 1H-phosphindole or dibenzophosphole substituents are suitable precursors for P/N-bi-heterosubstituted dimeric helicenes, as well as for new [6]- and [8]phosphahelicenes. The highly diastereoselective oxidative photocyclization of these olefins opens up access to enantiomerically pure helical derivatives. The structural characterization of a helical phosphine oxide, sulfide, and gold complex is reported. Copyright
