Calixaren-Rylen-Konjugate: Neue multichromophore Architekturen und Fluoreszenzsensoren für biologisch relevante Strukturen
Final Report Abstract
We succeeded to newly synthesize and fully characterize a variety of perylene bisimide - calix[4]arene arrays composed of up to three different types of perylene bisimide chromophores (orange, red and green PBIs) connected to each other by calix[4]arene spacers via the N-imide bond of the perylene bisimide moiety. Due to the specific optical properties of the individual chromophoric units and their defined spatial orientation provided by the calix[4]arene spacers, very efficient energy-transfer processes do occur from the orange perylene bisimide chromophoric unit to the red chromophoric unit, and from the red FBI moiety to the green dye unit within these systems, respectively. The efficiency of the transfer process is substantially influenced by the exact position of the orange, red and green chromophoric units with respect to each other. The photoinduced processes are studied with time resolved emission and femtosecond transient absorption spectroscopy. A quantitative analysis of the photophysical processes as well as their rates have been obtained by using UV/Vis absorption, steady-state and time-resolved emission, femtosecond transient absorption spectroscopy, spectrotemporal analysis of the femtosecond transient absorption data, and a theoretical analysis of the rates of the processes. Furthermore, a series of three wide rim perylene derivatives substituted by orange, red and green perylene bisimide units was prepared employing a diamino-calix[4]arene fixed in the 1,3-alternate conformation. These compounds are expected to be less flexible and thus might provide stronger interactions of the attached dye units with each other. The newly synthesized derivatives were characterized by lH-NMR spectroscopy and will be further investigated with respect to their optical and excited state properties Finally, the functionalization of the calix[4]arene scaffold with a melamine sensing unit and FBI chromophores to achieve optical sensors has been an additional objective for this project. Unfortunately, we did not yet succeed to synthesize the target molecules for the purpose of optical sensing, thus we discussed here briefly our synthetic efforts made.
Publications
- Org. Lett. 2002, 4, 2901-2904
M. O. Vysotsky, V. Böhmer, F. Würthner, C.-C. You, K. Rissanen
- Multichromophoric Cascades of Perylene Bisimide Dyes: Synthesis and Optical Properties. 2005, 19. Vortragstagung der Fachgruppe Photochemie der GDCh, Jena, Germany
C. Hippius, M. O. Vysotsky, V. Böhmer, F. Würthner
- Multichromophoric Cascades of Perylene Bisimide Dyes: Synthesis and Optical Properties. 2005, Calix 2005 - 8th International Conference on Calixarenes, Prague, Czech Republic
C. Hippius, M. O. Vysotsky, V. Böhmer, F. Würthner
- Multichromophoric Cascades of Perylene Bisimide Dyes: Synthesis and Optical Properties. 2005, ESF Conference on Supramolecular Chemistry, Obernai, France
C. Hippius, M. O. Vysotsky, V. Böhmer, F. Würthner
- Org. Biomol. Chem. 2005, 3, 172 - 184
C. Danila, M. Bolte, V. Böhmer
- Energy and Electron Transfer Processes in Multichromophoric Perylene Bisimide Dye Arrays and Aggregates. Mons, Belgien, 25.10.2006
F. Würthner
- Energy Transfer in Calix[4]arene-Based Cofacial Positioned Perylene Bisimide Arrays. 2006, 111th International BASF summer course, Ludwigshafen, Germany
C. Hippius, F. Schlosser, M. O. Vysotsky, V. Böhmer, F. Würthner
- Energy Transfer in Calix[4]arene-Based Cofacial Positioned Perylene Bisimide Arrays. 2006, HRSMC Symposium, Leiden, The Netherlands
C. Hippius, F. Schlosser, M. O. Vysotsky, V. Böhmer, F. Würthner
- Energy Transfer in Calix[4]arene-Based Cofacial Positioned Perylene Bisimide Arrays. 2006, OrChem 2006, Bad Nauheim, Germany
C. Hippius, F. Schlosser, M. O. Vysotsky, V. Böhmer, F. Würthner
- J. Am. Chem. Soc. 2006,128,3870-3871
C. Hippius, F. Schlosser, M. O. Vysotsky, V. Böhmer, F. Würthner
- Ph.D. Thesis, Universität Mainz, 2006
Crenguta Dordea
- Photoluminescent Arrays and Aggregates Based on Perylene Bisimide Dyes. LMU München, Physik, BMO Seminar und SFB 533 Kolloquium, 21.11.2006
F. Würthner
- Photoluminescent Arrays and Aggregates Based on Perylene Bisimide Dyes. XXI IUPAC Symposium on Photochemistry, Kyoto/Japan, 3.4.2006
F. Würthner
- Supramolecular Perylene Dye Chemistry: Functional Assemblies and Materials Inspired by Nature. 35th Scottish RSC Meeting, 18.12.2006, Heriot-Watt University
F. Würthner
- Supramolecular Perylene Dye Chemistry: Functional Molecular Assemblies and Materials. University of Amsterdam, Van 't Hoff Institute for Molecular Sciences, 27.10.2006, John van Geuns Lecture
F. Würthner
