[Nat. Commun.] 我室曹晓宇教授发表论文:Unveiling how intramolecular stacking modes of covalently linked dimers dictate photoswitching properties

2019年12月13日

我室曹晓宇教授在 Nat. Commun. 上发表论文:Unveiling how intramolecular stacking modes of covalently linked dimers dictate photoswitching properties

文章链接:https://www.nature.com/articles/s41467-019-13428-3

摘要:

Covalently linked π-stacked dimers represent the most significant platform for elucidating the relationship between molecular alignments and their properties. Here, we present the one-pot synthesis of two intramolecularly π-stacked dimers and disclose how intramolecular stacking modes dictate photoswitching properties. The dimer, which features cofacially stacked chromophores and geometrically favours intramolecular photochemical [2 + 2] cycloadditions, displays a nearly irreversible photoswitching behaviour. By contrast, the dimer, bearing crosswise stacked chromophores, is geometrically unfavourable for the cycloaddition and exhibits a highly reversible photoswitching process, in which the homolysis and reformation of carbon−carbon single bonds are involved. Moreover, the chiral carbon centres of both dimers endow these photoswitches with chirality and the separated enantiomers exhibit tuneable chiroptical properties by photoswitching. This work reveals that intramolecular stacking modes significantly influence the photochemical properties of π-stacked dimers and offers a design strategy toward chiral photoswitchable materials.