Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids.
32-Hetero-5,6-dimethoxyphenanthrisapphyrins-macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins-were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5-bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π-electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X-ray structural analyses, and supported by DFT calculations. Although protonation does not change their π-conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32-hetero-5,6-dioxophenanthrisapphyrins.
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Bartosz
B
Szyszko
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Marcin
M
Małecki
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Anna
A
Berlicka
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Michał J
MJ
Białek
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Agata
A
Białońska
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Kamil
K
Kupietz
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Ewa
E
Pacholska-Dudziak
Department of Chemistry, University of Wrocław, ul.14 F. Joliot-Curie, 50-383, Wrocław, Poland. lechoslaw.latos-grazynski@chem.uni.wroc.pl.
Lechosław
L
Latos-Grażyński
D018360:Crystallography, X-Ray; D008968:Molecular Conformation; D015394:Molecular Structure; D010616:Phenanthrenes / Q000138:chemical synthesis* / Q000737:chemistry; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry
D010616:Phenanthrenes; D011166:Porphyrins; C440448:sapphyrin; C031181:phenanthrene
density functional calculations; macrocycles; phenanthrenes; porphyrinoids; sapphyrin