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Molecules 2014, 19(4), 5278-5300; doi:10.3390/molecules19045278

Thermodynamics and Kinetics of Guest-Induced Switching between “Basket Handle” Porphyrin Isomers

, , , , , *  and
Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, Nijmegen 6525 AJ, The Netherlands
* Author to whom correspondence should be addressed.
Received: 10 March 2014 / Revised: 14 April 2014 / Accepted: 17 April 2014 / Published: 23 April 2014
(This article belongs to the Special Issue Molecular Switches)
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The 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.
Keywords: molecular switches; porphyrins; host-guest chemistry; viologens molecular switches; porphyrins; host-guest chemistry; viologens
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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.

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