Synthetic access and luminescence tuning in a series of β-H and β-silyl substituted phospholes
Synthetic access and luminescence tuning in a series of β-H and β-silyl substituted phospholes
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DOI：
10.1016/j.dyepig.2020.108443
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发表时间：
2020-09-01
影响因子：
4.5
通讯作者：
Pietschnig, Rudolf
中科院分区：
文献类型：
--
作者：
Klintuch, Dieter;Kirchmeier, Andreas;Pietschnig, Rudolf
从取代的1，3-二炔出发，探索了一种直接合成磷杂环戊烯的方法，得到了一系列贫电子和富电子取代基（C6 H5，C6 H4 CF 3，C6 F4 OCH 3，C5 H4 N，C4 H3 S，C4 H3 O，C6 H4 OCH 3）。该反应涉及PhPTMSLi与二炔的形式加成，导致相应的β-甲硅烷基磷杂环戊二烯在α-位上带有二炔的取代基。随后的脱甲硅烷基化得到相应的β-H取代的磷杂环戊烯，否则难以获得或无法获得。β-H磷光洞显示出有吸引力的发光特性，包括高量子产率。它们的β-甲硅烷基类似物在它们的吸收带中显示出由于位阻排斥而导致的在甲硅烷基单元附近的相邻环的共面性降低的结果。根据固态结构数据、量子化学密度泛函理论计算和实验紫外维斯及发光光谱建立了结构-性质关系。使用多核NMR、质谱法、元素分析和XRD（如果可用）确定所有新化合物的身份。
Starting from substituted 1,3-diynes a straightforward strategy to prepare phospholes has been explored for a series of substituents with electron poor and electron rich character (C6H5, C6H4CF3, C6F4OCH3, C5H4N, C4H3S, C4H3O, C6H4OCH3). The reaction involves formal addition of PhPTMSLi to the diyne resulting in the respective beta-silyl phosphole bearing the substituents of the diyne in the a-positions. Subsequent desilylation afforded the corresponding beta-H substituted phospholes which otherwise are difficult to obtain or inaccessible. The beta-H phospholes showed attractive luminescence features including high quantum yields. Their beta-silyl analogs revealed hypsochromic shifts in their absorption bands as a consequence of reduced coplanarity of the adjacent rings in vicinity of the silyl unit owing to steric repulsion. The structure property relationship was established on structural data from the solid state, quantum chemical DFT calculations and experimental UV vis and luminescence spectra. The identity of all new compounds was established using multinuclear NMR, mass spectrometry, elemental analysis and XRD where available.