Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, Colorado, 80309 (USA).
National Renewable Energy Laboratory, Golden, Colorado 80401 (USA).
Chemistry. 2015 Nov 16;21(47):16935-40. doi: 10.1002/chem.201502848. Epub 2015 Sep 30.
A series of phenylene vinylene macrocycles (PVMs) bearing substituents with various sizes and electronic properties have been synthesized through a one-step acyclic diene metathesis macrocyclization approach and their aggregation behaviors have been investigated. In great contrast to the aggregation of the analogous phenylene ethynylene macrocycles, which aggregate only when substituted with electron-withdrawing groups, these PVMs undergo exceptionally strong aggregation, regardless of the electron-donating or -withdrawing characters of the substituents. The unusual aggregation behavior of the PVMs is further investigated with thermodynamic and computer modeling studies, which show a good agreement with the recently proposed direct through-space interaction model, rather than the polar/π model. The high aggregation tendency of PVMs suggests the great potential of this novel class of shape-persistent macrocycles in a variety of applications, such as ion channels, host-guest recognition, and catalysis.
一系列带有不同大小和电子性质取代基的苯乙炔大环（PVMs）已经通过一步非循环二烯复分解大环化方法合成，并研究了它们的聚集行为。与类似的苯乙炔大环的聚集行为形成鲜明对比的是，只有当取代基为吸电子基团时，这些 PVMs 才会发生聚集，而无论取代基是供电子还是吸电子。通过热力学和计算机建模研究进一步研究了 PVMs 的异常聚集行为，这与最近提出的直接通过空间相互作用模型而不是极性/π模型很好地吻合。PVMs 的高聚集倾向表明，这种新型形状保持大环在各种应用中具有很大的潜力，例如离子通道、主体识别和催化。
