双卟啉分子镊子的合成与性质：间隔基柔韧性对结合作用和超分子手性生成的影响

Synthesis and Properties of Bis-Porphyrin Molecular Tweezers: Effects of Spacer Flexibility on Binding and Supramolecular Chirogenesis.

作者信息

Blom Magnus, Norrehed Sara, Andersson Claes-Henrik, Huang Hao, Light Mark E, Bergquist Jonas, Grennberg Helena, Gogoll Adolf

机构信息

Department of Chemistry-BMC, Uppsala University, Uppsala S-75123, Sweden.

Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK.

出版信息

Molecules. 2015 Dec 23;21(1):E16. doi: 10.3390/molecules21010016.

DOI:10.3390/molecules21010016

PMID:26703562

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6274253/

Abstract

Ditopic binding of various dinitrogen compounds to three bisporphyrin molecular tweezers with spacers of varying conformational rigidity, incorporating the planar enediyne (1), the helical stiff stilbene (2), or the semi-rigid glycoluril motif fused to the porphyrins (3), are compared. Binding constants Ka = 10⁴-10⁶ M(-1) reveal subtle differences between these tweezers, that are discussed in terms of porphyrin dislocation modes. Exciton coupled circular dichroism (ECCD) of complexes with chiral dinitrogen guests provides experimental evidence for the conformational properties of the tweezers. The results are further supported and rationalized by conformational analysis.

摘要

比较了各种双氮化合物与三种具有不同构象刚性间隔基的双卟啉分子镊子的双位点结合情况，这些分子镊子分别包含平面烯二炔（1）、螺旋刚性芪（2）或与卟啉稠合的半刚性甘脲基序（3）。结合常数Ka = 10⁴ - 10⁶ M⁻¹揭示了这些镊子之间的细微差异，并根据卟啉错位模式进行了讨论。与手性双氮客体形成的配合物的激子耦合圆二色性（ECCD）为镊子的构象性质提供了实验证据。构象分析进一步支持了这些结果并使其合理化。