In this paper, we present the synthesis of S- and N-heterocyclic annelated di(perylene bisimide) with extraordinary doubly bowl-shaped structures. The structures of fused PBI bowls confirmed by singlecrystal X-ray structure analysis and temperature-dependent 1H NMR are realized by the introduction of the steric congestion in nonbay regions and by the concurrent formation of the five-membered heterorings strain in bay regions. On the basis of the geometry obtained from the X-ray analysis, the maximum POAV1 pyramidalization angle is found in N-heterocyclic annelated diPBI 7, as large as 4.7, indicating the formation of two PBI bowls with significant curvatures. Furthermore, to assist the electrochemical and spectroscopic characterization of the two bowl-shaped derivatives and to assess the influence of heteroatoms on the bowl curvature, quantum-chemically optimized atomic structures, electronic properties, and optical signatures were computed with density functional theory.
H. Qian, W. Yue, Y. Zhen, S. Di Motta, E. Di Donato, F. Negri, et al. (2009). Heterocyclic Annelated Di(perylene bisimide): Constructing Bowl-Shaped Perylene Bisimides by the Combination of Steric Congestion and Ring Strain. JOURNAL OF ORGANIC CHEMISTRY, 74, 6275-6282 [10.1021/jo901285k].
Heterocyclic Annelated Di(perylene bisimide): Constructing Bowl-Shaped Perylene Bisimides by the Combination of Steric Congestion and Ring Strain
DI MOTTA, SIMONE;NEGRI, FABRIZIA;
2009
Abstract
In this paper, we present the synthesis of S- and N-heterocyclic annelated di(perylene bisimide) with extraordinary doubly bowl-shaped structures. The structures of fused PBI bowls confirmed by singlecrystal X-ray structure analysis and temperature-dependent 1H NMR are realized by the introduction of the steric congestion in nonbay regions and by the concurrent formation of the five-membered heterorings strain in bay regions. On the basis of the geometry obtained from the X-ray analysis, the maximum POAV1 pyramidalization angle is found in N-heterocyclic annelated diPBI 7, as large as 4.7, indicating the formation of two PBI bowls with significant curvatures. Furthermore, to assist the electrochemical and spectroscopic characterization of the two bowl-shaped derivatives and to assess the influence of heteroatoms on the bowl curvature, quantum-chemically optimized atomic structures, electronic properties, and optical signatures were computed with density functional theory.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
