Repozytorium
Wyszukaj
Kolekcje
Inne
Highly strained nonclassical nanotube end-caps. A single-step solution synthesis from strain-free, non-macrocyclic precursors.
Autorzy
Rok wydania
2015
Czasopismo
Journal of the American Chemical Society
Numer woluminu
137
Strony
1643-1649
DOI
10.1021/ja511951x
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Nonclassical nanotube end-caps have been constructed from strain-free heterocyclic precursors using a one-step synthetic procedure, involving multiple nickel-mediated Ullmann couplings. These systems consist of tubular macrocyclic sections that are tightly capped on one side with a bridging benzene ring, forming deep, chemically accessible cavities. The end-caps are characterized by exceptionally high internal strain energies reaching 144 kcal/mol. The optical absorption and emission properties of these molecules show a marked dependence on conjugation length and geometrical factors. The mechanism of end-cap formation, investigated using DFT calculations, relies on precise timing of transmetalation and reductive elimination events.
Adres publiczny
http://dx.doi.org/10.1021/ja511951x