Thermodynamics and Kinetics of Guest-Induced Switching between “Basket Handle” Porphyrin Isomers
AbstractThe synthesis and switching properties of two “basket handle” porphyrin isomers is described. The cis-oriented meso-phenyl groups of these porphyrins are linked at their ortho-positons via benzocrown-ether-based spacers, which as a result of slow atropisomerization are located either on the same side of the porphyrin plane (cis), or on opposite sides (trans). In solution, the cis-linked isomer slowly isomerizes in the direction of the thermodynamically more stable trans-isomer. In the presence of viologen (N,N'-dialkyl-4,4'-bipyridinium) derivatives, which have different affinities for the two isomers, the isomerization equilibrium could be significantly influenced. In addition, the presence of these guests was found to enhance the rate of the switching process, which was suggested to be caused by favorable interactions between the positively charged guest and the crown ethers of the receptor, stabilizing the transition state energies of the isomerization reaction between the two isomers. View Full-Text
- Supplementary File 1:
Supplementary Materials (PDF, 533 KB)
Scifeed alert for new publicationsNever miss any articles matching your research from any publisher
- Get alerts for new papers matching your research
- Find out the new papers from selected authors
- Updated daily for 49'000+ journals and 6000+ publishers
- Define your Scifeed now
Deutman, A.B.C.; Woltinge, T.; Smits, J.M.M.; De Gelder, R.; Elemans, J.A.A.W.; Nolte, R.J.M.; Rowan, A.E. Thermodynamics and Kinetics of Guest-Induced Switching between “Basket Handle” Porphyrin Isomers. Molecules 2014, 19, 5278-5300.
Deutman ABC, Woltinge T, Smits JMM, De Gelder R, Elemans JAAW, Nolte RJM, Rowan AE. Thermodynamics and Kinetics of Guest-Induced Switching between “Basket Handle” Porphyrin Isomers. Molecules. 2014; 19(4):5278-5300.Chicago/Turabian Style
Deutman, Alexander B.C.; Woltinge, Tim; Smits, Jan M.M.; De Gelder, René; Elemans, Johannes A.A.W.; Nolte, Roeland J.M.; Rowan, Alan E. 2014. "Thermodynamics and Kinetics of Guest-Induced Switching between “Basket Handle” Porphyrin Isomers." Molecules 19, no. 4: 5278-5300.