当前位置: X-MOL 学术Chem. Mater. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Side Chain Regioisomers that Dictate Optical Properties and Mechanofluorochromism through Crystal Packing
Chemistry of Materials ( IF 8.6 ) Pub Date : 2020-05-18 , DOI: 10.1021/acs.chemmater.0c01676
Seth A. Sharber 1, 2 , Samuel W. Thomas 1
Affiliation  

Designing strong interactions into π-conjugated materials can direct their typically uncontrolled molecular packing and is an important strategy toward tuning their technologically relevant properties in the solid state. Here we demonstrate unconventional control over solid-state fluorescence and mechanofluorochromism (MFC) through regiochemical substitutions in side chains of 12 three-ring phenylene ethynylenes (PEs) that employ fluoroarene–arene (ArF–ArH) interactions between tetrafluoro ArF pendants and PE main chains to direct crystal packing, with single-atom variations of the lone proton in ArF pendants between 4-hydro, 5-hydro, and 6-hydro substitution yielding in two cases dramatically different fluorescence and MFC behavior. X-ray crystal structures reveal key intermolecular interactions of ArF rings, including their lone protons, which vary as a function of substitution pattern and contribute to optical properties in solids. Rarely reported, particularly with such dramatic results, this systematic study on regiochemical effects over solid-state properties demonstrates the versatility of using discrete, directional interactions of side chains for noncovalent control in conjugated materials.

中文翻译:

侧链区域异构体可通过晶体堆积来决定光学性质和机械氟致变色

在π共轭材料中设计强相互作用可以指导其通常不受控制的分子堆积,并且是调整其固态技术相关性能的重要策略。在这里,我们证明了通过在12个三环亚苯基亚乙炔基(PE)的侧链中进行区域化学取代,对固态荧光和机械氟代变色(MFC)进行非常规控制,这些三环亚苯基亚乙炔基在四氟ArF侧基和PE主链之间采用了氟芳烃-芳烃(ArF-ArH)相互作用在两种情况下,荧光和MFC行为截然不同,ArF侧链中的单个质子在4-氢,5-氢和6-氢取代之间发生单原子变化,从而直接指导晶体堆积。X射线晶体结构揭示了ArF环的关键分子间相互作用,包括其孤子质子,它们随取代图案的变化而变化,并有助于固体中的光学性能。很少有报道,特别是具有如此引人注目的结果,这项关于区域化学作用对固态性质的系统研究证明了使用侧链的离散,定向相互作用在共轭材料中进行非共价控制的多功能性。
更新日期:2020-07-14
down
wechat
bug