Polycationic States of Oligoanilines Based on Wurster's Blue

• Published in: European Journal of Organic Chemistry Vol. 2009; no. 26; pp. 4441 - 4450
• Main Authors: Ito, Akihiro, Sakamaki, Daisuke, Ino, Haruhiro, Taniguchi, Aya, Hirao, Yasukazu, Tanaka, Kazuyoshi, Kanemoto, Katsuichi, Kato, Tatsuhisa
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag 01-09-2009; Wiley-VCH
• Subjects: Chemistry; EPR spectroscopy; Exact sciences and technology; Free radicals chemistry; Magnetic properties; Noncondensed benzenic compounds; Organic chemistry; Oxidation; Preparations and properties; Radical ions; Reactivity and mechanisms; Redox chemistry; Intramolecular reaction; Chemical solution; EPR spectrometry; Stepwise mechanism; Aniline derivatives; Oxidant; Characterization; Phenylenediamine; Radical ions; Polycation; Organic free radical; Benzenic compound; Oxidation; Redox chemistry; Redox system; EPR spectroscopy; Magnetic properties
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200900403

Polycations of two oligoanilines based on Wurster's blue,N,N′,N″‐tris[4‐(dimethylamino)phenyl]‐N,N′,N″‐trimethyl‐1,3,5‐benzenetriamine (2) and N,N′‐bis(3‐{N‐[4‐(dimethylamino)phenyl]‐N‐methylamino}phenyl)‐N,N′‐dimethyl‐p‐phenylenediamine (3), have been generated efficiently by a stepwise oxidation procedure. Their redox behavior was characterized in terms of the embedded p‐phenylenediamine (PD) units and their intramolecular connectivity. EPR analysis of the oxidized 2 and 3 species revealed the existence of high‐spin species in solution. It was found that spin multiplicities of the dominant polycationic species of 2 and 3 formed by 3 equiv. of oxidant can be assigned to quartet and doublet states, respectively on the basis of pulsed EPR spectroscopy. These results demonstrate that the intramolecular connectivity between the spin‐containing units decisively influences the spin preference of the multispin systems based on oligoanilines.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
The spin multiplicities of the dominant species of two oligoanilines based on Wurster's blue generated by three equivalents of oxidant have been found to exist as quartet and doublet states at low temperatures.These results demonstrate that the intramolecular connectivity between the spin‐containing units decisively influences the spin preference of the multispin systems based on oligoanilines.