Conformational restriction of flexible molecules in solution by a semirigid bis-porphyrin molecular tweezer

TETRAHEDRON

卷:69

Article

Norrehed, Sara¹  Polavarapu, Prasad¹  Yang, Wenzhi¹  Gogoll, Adolf¹  Grennberg, Helena¹ 

[1] Uppsala Univ, Dept Chem BMC, S-75123 Uppsala, Sweden

关键词: Conformational analysis;    NMR spectroscopy;    Host-guest systems;    Supramolecular chemistry;    Porphyrinoids;   

DOI  :  10.1016/j.tet.2013.06.013

来源: Elsevier

【 摘 要 】

A semirigid bis-porphyrin molecular clip with a glycoluril backbone has been synthesized. The clip provides an adaptable molecular cavity for binding of diamines. Binding constants for diamines of 10(4)-10(7) M-1 are orders of magnitude higher than those for monoamines of 10(3) M-1, indicating a preference to bidentate binding. NMR studies confirmed that binding of bidentate guests occurs inside the clip. Short- and medium-size acyclic molecular guests are locked into a single, extended conformation, and also guests with longer flexible chains exhibit considerably less conformational mobility than when free in solution. The size of the cavity adapts to the guest size, as indicated by modelling studies and self diffusion constants of the complexes. (C) 2013 Elsevier Ltd. All rights reserved.

【 授权许可】

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