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Synthesis 2009(5): 848-852  
DOI: 10.1055/s-0028-1083374
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Dendritic Triphenylmethylium and Tetraphenylmethane Compounds

Herbert Meier*, Soungkyoo Kim, Annette Oehlhof
Institute of Organic Chemistry, , University of Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
Fax: +49(6131)39225396; e-Mail: hmeier@mail.uni-mainz.de;
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Publication History

Received 23 September 2008
Publication Date:
11 February 2009 (online)

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Abstract

Stilbenoid dendrimers possessing a methanol or methane core are prepared using Wittig-Horner reactions. The dendritic tris(stilbenyl)carbinols 3a-c are converted into the corresponding methylium salts 3′a-c on treatment with trifluoroacetic or tetrafluo­roboric acid. The extended cross-conjugation in the dendritic methylium ion 3′c results in a long-wavelength absorption (λmax = 697 nm) whereas the conjugated model systems 3′a and 3′b are red-shifted (λmax = 772 nm and 748 nm, respectively). Charge delocalization in the cations is evident from the low-field shifts of the ¹³C NMR signals. In contrast to the dark-blue dyes 3′a-c, the tris(stilbenyl)carbinols and tetrakis(stilbenyl)methane derivatives 3a-c and 7 exhibit long-wavelength absorption bands in the UV region.

Key words

stilbene - charge delocalization - Wittig-Horner reaction - olefination - dendrimers - dyes

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12

Due to the equilibration, the intensity of the band depends on the ratio of 3/CF3COOH. The λmax values are somewhat blue-shifted by a high CF3COOH concentration. We assign this effect to a decrease of push-pull character due to increasing protonation of the alkoxy groups.