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Synthesis and Optical Properties of all‐ trans ‐Oligodiacetylenes
Author(s) -
Pilzak Gregor S.,
van Lagen Barend,
Hendrikx Cindy C. J.,
Sudhölter Ernst J. R.,
Zuilhof Han
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800241
Subject(s) - trimer , elongation , monomer , fluorescence , absorption (acoustics) , quantum yield , oligomer , yield (engineering) , chemistry , solvent , wavelength , crystallography , photochemistry , analytical chemistry (journal) , materials science , polymer , polymer chemistry , optics , chromatography , dimer , organic chemistry , physics , optoelectronics , metallurgy , composite material , ultimate tensile strength
A new series of pure and highly soluble oligodiacetylenes (ODAs) was synthesized in high yield and on a multi‐milligram scale by a sequence of Sonogashira reactions with a strongly reduced level of homocoupling. The λ max and ε max of these ODAs show an increase with both chain elongation and solvent polarity. A plot of λ max absorption versus 1/CL (CL=conjugation length) was shown to be linear. The λ max converges to 435 nm for the longest members of the series at micromolar concentration. This reveals that the longest wavelength absorption observed for PDA chains ( λ max up to 700 nm) is due to aggregation effects. The fluorescence quantum yield increased from monomer to trimer and decreased for longer ODAs. A similar trend is found for the lifetime of fluorescence with a maximum of 600 ps for the trimer. The observed linearity of the rotational correlation time with the oligomer length implies that the ODA chains in solution lack significant geometrical changes. This implies that the ODAs in solution are fully stretched molecular rods of up to 4 nm in length.