title: Synthesis and Properties of Rhomboidal Macrocyclic Subunits of Graphdiyne-Like Nanoribbons.
abstract: 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.
authors.affiliation: Département de Chimie and Centre de Recherche sur les Matériaux Avancés (CERMA) and ‡Département de Chimie and Centre en Catalyse et Chimie Verte (C3V), Université Laval , 1045 Ave de la Médecine, Québec, Canada G1V 0A6.
authors.forename: Maude
authors.initials: M
authors.lastname: Desroches
authors.affiliation: Département de Chimie and Centre de Recherche sur les Matériaux Avancés (CERMA) and ‡Département de Chimie and Centre en Catalyse et Chimie Verte (C3V), Université Laval , 1045 Ave de la Médecine, Québec, Canada G1V 0A6.
authors.forename: Marc-André
authors.initials: MA
authors.lastname: Courtemanche
authors.affiliation: Département de Chimie and Centre de Recherche sur les Matériaux Avancés (CERMA) and ‡Département de Chimie and Centre en Catalyse et Chimie Verte (C3V), Université Laval , 1045 Ave de la Médecine, Québec, Canada G1V 0A6.
authors.forename: Geneviève
authors.initials: G
authors.lastname: Rioux
authors.affiliation: Département de Chimie and Centre de Recherche sur les Matériaux Avancés (CERMA) and ‡Département de Chimie and Centre en Catalyse et Chimie Verte (C3V), Université Laval , 1045 Ave de la Médecine, Québec, Canada G1V 0A6.
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Morin