Synthesis and Properties of Rhomboidal Macrocyclic Subunits of Graphdiyne-Like Nanoribbons

Autor:	Marc-André Courtemanche, Maude Desroches, Geneviève Rioux, Jean-François Morin
Rok vydání:	2015
Předmět:	chemistry.chemical_classification Band gap Organic Chemistry Alkyne Ring (chemistry) Metal Delocalized electron Crystallography Atomic orbital chemistry visual_art visual_art.visual_art_medium Molecule Organic chemistry HOMO/LUMO
Zdroj:	The Journal of Organic Chemistry. 80:10634-10642
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.5b01752
Popis:	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.
Databáze:	OpenAIRE
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