Synthesis and Electronic Properties of Sterically Demanding N-Arylphenothiazines and Unexpected Buchwald−Hartwig Aminations

Autor:	Thomas Müller, Adam W. Franz, Frank Rominger
Rok vydání:	2008
Předmět:	Models Molecular Steric effects Aryl Organic Chemistry Chromophore Photochemistry chemistry.chemical_compound chemistry Phenothiazines Phenothiazine Excited state Organic chemistry Oxidative coupling of methane Amines Cyclic voltammetry Perylene
Zdroj:	The Journal of Organic Chemistry. 73:1795-1802
ISSN:	1520-6904 0022-3263
DOI:	10.1021/jo702389v
Popis:	Phenothiazine is coupled under Buchwald-Hartwig conditions with bromo anthracenes and perylene as substrates to give phenothiazine-anthracene and phenothiazine-perylene dyads and triads. Investigation of the electronic properties of these sterically demanding N-aryl phenothiazines by absorption and emission spectroscopy, cyclic voltammetry, and DFT calculations revealed that the individual chromophores are decoupled in the electronic ground state but show unique electronic communication in the excited state. For the anthracenyl-bridged diphenothiazine an intense electronic coupling of the phenothiazinyl units is detected upon oxidation. Besides, attempts to synthesize phenothiazine compounds with even more sterically demanding aryl substituents in the 10-position under N-arylation conditions gave rise to the formation of quite unexpected products of arylation and/or oxidative coupling. The folding angle of the phenothiazine in a consanguineous series correlates well with the first oxidation potential.
Databáze:	OpenAIRE
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