multi-step redox systems with nir-fluorescence based on 4h-imidazoles多步氧化还原系统与基于4 h-imidazoles nir-fluorescence.pdfVIP

Molecules 2007, 12, 723-734 molecules ISSN 1420-3049 Full Paper Multi-step Redox Systems with NIR-Fluorescence Based on 4H-Imidazoles Martin Matschke and Rainer Beckert* Institute of Organic and Makromolecular Chemistry, Friedrich-Schiller University D-07743 Jena, Humboldtstr. 10, Germany * Author to whom correspondence should be addressed; E-mail: c6bera@uni-jena.de; Tel.: (+049) 3641 948 230; Fax: (+049) 3641 948 212 Received: 22 March 2007; in revised form: 29 March 2007 / Accepted: 29 March 2007 / Published: 5 April 2007 Abstract: A new class of 4H-imidazoles was synthesized starting from fused-ring aromatic dinitriles. Strong bathochromic shifts of the longest wavelength absorptions were observed in the corresponding UV/vis spectra due to a conversion of the merocyanine chromophores into cyanines/(aza)oxonoles upon protonation/deprotonation of the 4H- imidazoles. Novel boratetraazapentalenes were synthesized via a cyclization reaction with boron trifluoride. These mesoionic species bearing a cyanine chromophore not only show NIR-fluorescence, they also participate as part of a quasi-reversible multi-step redox system. Large calculated semiquinone formation constants KSEM (3x1010 to 5x1011) indicate a high thermodynamic stability of the corresponding radical anions (SEM). Keywords: 4H-Imidazoles, boratetraazapentalenes, multi-step redoxsystems, NIR- fluorescence. Introduction Over the last several years a great number of organic substances with extrao