Modulation of the optical properties of soluble N-alkylated 4-pyridyl diketopyrrolopyrrole derivatives
Modulation of the optical properties of soluble N-alkylated 4-pyridyl diketopyrrolopyrrole derivatives
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DOI：
10.1016/j.dyepig.2021.109836
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发表时间：
2022-01
影响因子：
4.5
通讯作者：
J. Humphreys;Ferdinando Malagreca;P. Hume;W. Lewis;E. Davies;S. Argent;D. Amabilino
中科院分区：
文献类型：
--
作者：
J. Humphreys;Ferdinando Malagreca;P. Hume;W. Lewis;E. Davies;S. Argent;D. Amabilino
报道了N-烷基化3，6-二（吡啶-4-基）-2，5-二氢吡咯并[3，4-c]吡咯-1，4-二酮（PyrDPNH）衍生物在溶液和固体中的吸收和荧光性质，并沿着研究了这些性质在不同酸碱度下的变化.以PyrDPPNH为原料合成了具有己基（PyrDPPN-Hex）和甲氧基乙氧基乙基（PyrDPPN-Hex）链的化合物，得到了高溶解性的染料。此外，还分离了单取代衍生物。探索了一系列溶剂，以了解它们在从有机电子到传感器的应用中的潜在用途。在光学上，染料是高度荧光的，并且由于N-烷基化破坏氢键网络，在固态下发射具有大的斯托克斯位移。链的性质决定了材料的π相互作用和堆积，导致固态吸收光谱和从晶体结构预测的理论迁移率的调制。甲氧基乙氧基乙基链扭曲的平面和弯曲，以允许相当大的分子重叠和小的发色团间位移与parentPyrDPNH惊人相似的π相互作用，导致H型聚集的吸收带的贡献和一个数量级的改善理论流动性相比，己基类似物。与此相反，PyrDPPN-受阻胺在吡啶基和内酰胺单元之间具有扭曲的CH-π相互作用，具有更大的分子位移，表现为对吸收带的主要J-聚集贡献和适度的迁移率。结果强调了侧链修饰的潜力，并显示了柔性极性链的潜在益处的结构证据。吡啶环上的氮原子孤对电子能在酸性环境中被质子化，产生一种光度响应，表明其作为质子传感器的潜力。单取代的化合物对碱和酸都有响应，使它们对分子逻辑应用感兴趣。
The absorption and fluorescence properties ofN-alkylated 3,6-di (pyridin-4-yl)-2,5-dihydropyrrolo [3,4-c]pyrrole-1,4-dione (PyrDPPNH) derivatives in solution and the solid state are reported, along with the modulation of these properties under varying acidity or basicity. The compounds with hexyl (PyrDPPN-Hex) and methoxy ethoxy ethyl (PyrDPPN-MEE) chains were synthesised fromPyrDPPNHgiving highly soluble dyes. In addition, the mono-substituted derivatives were also isolated. A range of solvents was explored to provide understanding regarding their potential use in applications ranging from organic electronics to sensors. Optically the dyes are highly fluorescent and, as a result of N-alkylation breaking the hydrogen bond network, emissive in the solid state with large Stokes shifts. The nature of the chain dictates the π interactions and packing of the materials, resulting in modulation of the solid-state absorption spectra and theoretical mobility predicted from the crystal structures. The methoxy ethoxy ethyl chain twists out of the plane and bends to allow considerable molecular overlap and small interchromophore displacement with strikingly similar π interactions to the parentPyrDPPNH, resulting in a contribution ofH-type aggregation to the absorption band and an order of magnitude improvement in theoretical mobility compared with the hexyl analogue. In contrast,PyrDPPN-Hexpossesses a distorted CH-π interaction between pyridyl and lactam units, with greater molecular displacement manifesting in dominantJ-aggregation contribution to absorption band and moderate mobility. The results emphasise the potential for sidechain modification and show structural evidence for the potential benefits of the flexible polar chains. The nitrogen lone pair of the pyridyl ring can be protonated in acidic environment to produce a photometric response suggesting potential as a proton sensor. The mono-substituted compounds are responsive to both base and acid, making them interesting for molecular logic applications.