Reversible adaptation to photoinduced shape switching by oligomer-macrocycle interconversion with component selection in a three-state constitutional dynamic system.
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Date publication
décembre 2014
Auteurs
Membres identifiés du Cancéropôle Est :
Pr LEHN Jean-Marie
Tous les auteurs :
Vantomme G, Lehn JM
Lien Pubmed
Résumé
Light irradiation of the molecular photoswitch 1-E causes isomerization into the 1-Z configuration stabilized by an internal hydrogen bond. 1-E bears aldehyde groups allowing for dynamic covalent reaction with linear diamines. On photoinduced E/Z shape switching of 1 in presence of diamines, the system undergoes interconversion between two states, a non-cyclic oligomeric one and a macrocyclic one, corresponding respectively to the E and Z configurations of 1. With a mixture of linear alpha,omega-diamines, 1-E yields non-selective dynamic oligomers by random incorporation of diamine components. Photoswitching to the 1-Z form leads to constitutional adaptation with preferential formation of the macrocycle incorporating the best suited diamine, H2 N(CH2 )7 NH2 . In presence of metal cations, the E form switches from its unbound W shape to its coordinated U shape and yields the macrocycle resulting from the selective incorporation of the diamine H2 NCH2 CH2 OCH2 CH2 NH2 that contains an additional O coordination site. Taken together, the results obtained describe constitutional adaptation in a triple state system: an oligomeric one and two different macrocyclic ones generated in response to two orthogonal agents, a physical stimulus, light, or a chemical effector, metal cations. These three states present, towards the incorporation of diamine components, respectively no selection, photoselection and metalloselection.
Référence
Chemistry. 2014 Dec 1;20(49):16188-93