The photoinduced dynamics of a dithienylethene chromophore coupled to the surface of TiO(2) by either a tripodal linker or a carboxyl group was investigated with ultrafast transient absorption spectroscopy. The absence of electron transfer from the photoexcited tripodal dithienylethene chromophore demonstrates that the tripod efficiently uncouples the electronic systems of dithienylethene and TiO(2). Contrary to this situation, photoinduced electron transfer can compete with ultrafast intramolecular relaxation in the COOH-dithienylethene/TiO(2) coupled system. An electron transfer rate of 1.1 × 10(12) s(-1) can be extracted, which is considerably slower than the intramolecular relaxation rate of the dithienylethene (3.7 × 10(12) s(-1)). Consequently, the electron transfer reaction exhibits a low efficiency.

SummaryPhotochromic pyrans for applications in material and life sciences were synthesized via palladium-mediated cyanation, carbonylation and Sonogashira cross-coupling starting from bromo-substituted naphthopyran 1 and benzopyrans 2a/b. A novel photoswitchable benzopyran-based ω-amino acid 6 for Fmoc-based solid-phase peptide synthesis is presented. The photochromic behaviour of the 3-cyano-substituted benzopyran 5a was investigated by time-resolved absorption spectroscopy in the picosecond time domain.

SummaryPhotoswitchable peptides were synthesized by using cysteine- and auxiliary-based native chemical ligation reactions. For this purpose, the two regioisomeric azobenzene building blocks 3,4'-AMPB thioester 1b and 4,4'-AMPB thioester 2b were employed in the ligation reactions. While 4,4'-AMPB requires the 4,5,6-trimethoxy-2-mercaptobenzyl auxiliary to minimize reduction of the diazene unit, 3,4'-AMPB can be used in combination with the 4,5,6-trimethoxy-2-mercaptobenzyl auxiliary as well as the N α-2-mercaptoethyl auxiliary. Thus, 3,4'-AMPB derivatives/peptides proved to be significantly less prone to reduction by aliphatic and aromatic thiols than were the 4,4'-AMPB compounds.