Synthesis of Hydroxyoligophenylenes Containing Electron-donating, Electron Accepting Groups, or π-Deficient Aromatic Ring and Their Solvatochromic Behavior
Synthesis of Hydroxyoligophenylenes Containing Electron-donating, Electron Accepting Groups, or π-Deficient Aromatic Ring and Their Solvatochromic Behavior
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含给电子基团、受电子基团或缺π芳香环的羟基低聚亚苯基的合成及其溶剂化变色行为
DOI：
10.1002/poc.3671
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发表时间：
2017
影响因子：
1.8
通讯作者：
R. Yamaji
中科院分区：
文献类型：
--
作者：
I. Yamaguchi;R. Yamaji
我们已经报道了一端有羟基的低聚（对苯基）s (OPPs)，即OPP(n)‐OHs（其中为苯环数）。OPPs表现出明显的溶剂变色；当用钠处理opp (n)‐OH时，OH基团的去质子化引起吸收最大值（λmax）的显色位移，该位移随溶剂的供体数（dn）的增加而增加。我们假设opp (n)‐ona5表现出的溶剂致变色是由于分子内电荷从苯氧基钠转移到相邻环。为了验证这一假设，通过Suzuki偶联反应合成了具有供电子二甲氨基（n= 3, R = NMe2）、供电子硝基（n= 3, R = NO2）和缺π吡啶环（n= 2, R = Py）的羟基低聚苯乙烯（R‐OPP(n)‐OH）。用NaH处理羟基的去质子化引起λmaxofR‐OPP(m)‐ONa的色移（Δλ）。去质子化物质的TheΔλ随溶剂的DNs增加而增加。r - OPP(m) - on2的发射峰位置与溶剂的dn有关；因此，可以通过改变溶剂来调整发射颜色。R‐OPP(m)‐oh3对OH基团和OPP单元进行了电化学氧化。有关r - OPP(n) - ona显着的溶剂致变色行为的数据将为开发新的发光材料提供有用的信息。
We have reported oligo(p‐phenylene)s (OPPs) with an OH group located at one end, namely,OPP(n)‐OHs(wherenis the number of benzene rings). The OPPs exhibited significant solvatochromism; the deprotonation of the OH groups ofOPP(n)‐OHs, when treated with NaH, caused a bathochromic shift of absorption maxima (λmax) that increased with the donor numbers (DNs) of the solvents. We assumed that the solvatochromism exhibited byOPP(n)‐ONawas attributed to an intramolecular charge shift from the sodium phenoxy group(s) to the adjacent rings. In this study, to investigate the assumption, hydroxyoligophenylenes (R‐OPP(n)‐OH) with an electron‐donating dimethylamino group (n= 3, R = NMe2), an electron‐accepting nitro group (n= 3, R = NO2), and a π‐deficient pyridine ring (n= 2, R = Py) were synthesized by the Suzuki coupling reaction. The deprotonation of the OH group of by treatment with NaH caused a bathochromic shift (Δλ) of λmaxofR‐OPP(m)‐ONa. TheΔλ of the deprotonated species increased with the DNs of the solvents. The emission peak positions ofR‐OPP(m)‐ONadepended on the DNs of the solvents; therefore, the emission color could be tuned by changing the solvent.R‐OPP(m)‐OHreceived an electrochemical oxidation of the OH group and OPP unit. The data related to the remarkable solvatochromic behavior ofR‐OPP(n)‐ONawill be useful information for the development of new luminescent materials.