Novel Photoswitchable Receptors: Synthesis and Cation-Induced Self-Assembly into Dimeric Complexes Leading to Stereospecific [2+2]-Photocycloaddition of Styryl Dyes Containing a 15-Crown-5 Ether Unit

Styryl dyes 4a-e containing a 15-crown-5 ether unit and a quinoline residue with a sulfonatoalkyl or sulfonatobenzyl N-substituent were synthesized. The relationship between the photochemical behavior of these dyes and their aggregates derived from complexation with Mg2+ in MeCN was studied using 1H NMR and absorption spectroscopy. The E-isomers of 4a-e were shown to form highly stable dimeric (2:2) complexes with Mg2+. Upon irradiation with visible light, the dimeric complexes undergo two competing photoreactions, viz., geometric E Z isomerization, resulting in an anion-capped 1:1 complex of the Z-isomer with Mg2+ and stereospecific syn-head-to-tail [2+2]-cycloaddition, affording a single isomer of bis-crown-containing cyclobutane. The N-substituent in the dye has a dramatic effect on the photochemical behavior of the dimeric complex. Molecular dynamics and semiempirical quantum-chemical calculations were carried out to interpret the observed photocycloaddition in the dimer. Conformational equilibria for the dimer of (E)-4b were analyzed using 1H NMR spectroscopy.

Ushakov, Evgeny N (författare)
Fedorova, Olga A (författare)
Baskin, Igor I (författare)
Buevich, Alexei V (författare)
Andryukhina, Elena N (författare)
Alfimov, Michael V (författare)
Johnels, DanUmeå universitet,Kemiska institutionen(Swepub:umu)dajo0001 (författare)
Edlund, UlfUmeå universitet,Kemiska institutionen(Swepub:umu)uled0001 (författare)
Whitesell, James K (författare)
Fox, Marye Anne (författare)
Umeå universitetKemiska institutionen (creator_code:org_t)

Ingår i:The Journal of Organic Chemistry: American Chemical Society (ACS)68:16, s. 6115-250022-32631520-6904

Av författaren/redakt...: Gromov, Sergey P; Ushakov, Evgeny ...; Fedorova, Olga A; Baskin, Igor I; Buevich, Alexei ...; Andryukhina, Ele ...; visa fler...; Alfimov, Michael ...; Johnels, Dan; Edlund, Ulf; Whitesell, James ...; Fox, Marye Anne; visa färre...

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