177500-67-3Relevant articles and documents
π-electron conjugation effects in antiaromatic dehydro[12]- and aromatic dehydro[18]-annulenes
Mitzel, Frieder,Boudon, Corinne,Gisselbrecht, Jean-Paul,Gross, Maurice,Diederich, Francois
, p. 2318 - 2319 (2002)
N,N-Dimethylanilino-substituted perethynylated dehydro[12]- and dehydro[18]-annulenes were prepared by oxidative acetylenic coupling of cis-bisdeprotected tetra-ethynylethene derivatives obtained by a new photochemical route; they display strongly bathoch
Photochemical trans-cis isomerisation of donor/acceptor-substituted (E)-hex-3-ene-1,5-diynes (1,2-diethynylethenes, DEEs) and 3,4-diethynylhex-3-ene-1,5-diynes (tetraethynylethenes, TEEs)
Martin, Rainer E.,Bartek, Johannes,Diederich, Francois,Tykwinski, Rik R.,Meister, Erich C.,Hilger, Anouk,Luethi, Hans Peter
, p. 233 - 241 (2007/10/03)
The photochemically reversible trans-cis isomerisation of (E)-hex-3-ene-1,5-diynes (1,2-diethynylethenes, DEEs) and 3,4-diethynylhex-3-ene-1,5-diynes (tetraethynylethenes, TEEs) substituted with electron-donating (p-dialkylaminophenyl) and/or electron-accepting (p-nitrophenyl) groups has been examined. The type and degree of donor/acceptor (D/A) functionalisation has been found to drastically affect the partial quantum yields of isomerisation Φt→c and Φc→t. Total quantum yields in n-hexane vary from Φtotal = 0.72 for a bis-acceptor substituted TEE to Φtotal, = 0.015 for a four-fold, bis-donor, bis-acceptor substituted TEE derivative. A strong relationship between Φtotal and solvent polarity as well as a strong dependence of Φt→c and Φc→t on the wavelength of excitation λexc has been observed. The temperature dependence of the photoisomerisation has been investigated for a bis-acceptor-substituted DEE and shows no changes in Φtotal over the temperature range 6.5-65 °C. None of the compounds studied undergoes thermal isomerisation at 27 °C in n-hexane. Further analysis of these compounds by theoretical investigations at the semiempirical level of theory reveals a significant reduction of the bond order of the central olefinic double bond in the D-D, D-A and A-A TEEs upon electronic excitation, thus ultimately facilitating photoisomerisation.