Controlling the canonical/zwitterionic balance through intramolecular proton transfer: a strategy for vapochromism†,Materials Chemistry Frontiers

当前位置： X-MOL 学术 › Mater. Chem. Front. › 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.)

Controlling the canonical/zwitterionic balance through intramolecular proton transfer: a strategy for vapochromism†
Materials Chemistry Frontiers ( IF 6.0 ) Pub Date : 2018-05-18 00:00:00 , DOI: 10.1039/c8qm00171e
Simon Pascal _{1,

2,

3,

4,

5} , Lucien Lavaud _{1,

2,

3,

4,

5} , Cloé Azarias _{6,

7,

8,

9,

10} , Gabriel Canard _{1,

2,

3,

4,

5} , Michel Giorgi _{11,

12,

13,

14,

15} , Denis Jacquemin _{6,

7,

8,

9,

10} , Olivier Siri _{1,

2,

3,

4,

5}

Affiliation

A series of N-substituted diamino-benzoquinone diimines featuring tunable aryl electron-withdrawing functions were synthesized. For the first time, the subtle variation of electronic richness allows controlling the canonical vs. zwitterionic equilibrium through the tuning of an intramolecular proton transfer. The establishment of a ground-state zwitterionic electronic structure, in lieu of the canonical one, within a monocyclic architecture is evidenced by the X-ray structure of one compound (4) and the telltale absorption spectra of the whole series that display an unexpected signature at low energy (ca. 700 nm). The evolution of this peculiar band is concomitant with the electron-withdrawing strength of the aryl substituents and theoretical calculations highlight that this band can be attributed to a charge transfer transition from the anionic cyanine towards the cationic cyanine. Finally, such a color change is advantageously used for the rapid and naked-eye detection of N,N-dimethylformamide using 3a as a vapochromic material. This latter experiment shows the first case of intramolecular solid-state proton transfer occurring in a polar environment.

中文翻译：

通过分子内质子转移控制经典/两性离子平衡：气相致变色的策略†

合成了一系列具有可调的芳基吸电子功能的N-取代的二氨基-苯醌二亚胺。电子丰富度的细微变化首次允许通过分子内质子转移的调节来控制经典与两性离子平衡。一种化合物的X射线结构（4）和显示出乎意料特征的整个系列的信号吸收光谱证明，在单环结构内建立了基态两性离子电子结构来代替典范结构。低能量（约700 nm）。该奇特谱带的发展与芳基取代基的吸电子强度同时发生，理论计算表明该谱带可归因于电荷从阴离子花青向阳离子花青的转移。最后，这种颜色变化有利地用于使用3a作为气相致变色材料对N，N-二甲基甲酰胺进行快速肉眼检测。后一个实验显示了在极性环境中发生分子内固态质子转移的第一种情况。

更新日期：2018-05-18

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文