Linear Extension of Anthracene via B←N Lewis Pair Formation: Effects on Optoelectronic Properties and Singlet O 2 Sensitization
Linear Extension of Anthracene via B←N Lewis Pair Formation: Effects on Optoelectronic Properties and Singlet O 2 Sensitization
复制标题
通过 B–N 路易斯对形成实现蒽的线性延伸：对光电性质和单线态 O 2 敏化的影响
DOI：
10.1002/anie.202113075
复制
发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Jäkle, Frieder
中科院分区：
文献类型：
--
作者：
Vanga, Mukundam;Sahoo, Ashutosh;Lalancette, Roger A.;Jäkle, Frieder
通过B←N Lewis对形成的多环芳烃（PAHs）功能化提供了一个机会，可以明智地微调结构特征和光电性能，以适应有机电子器件、生物成像和单线态氧生成的增敏剂的应用需求。我们证明了2,6 -二（pyrid - 2 - yl）蒽的N向亲电硼化反应可以得到线性扩展的蒽衍生物espy - BR（R=Et, Ph, C6F5）。与茚合9,10 -二苯基镧相比，py - br1中正式的“BN for CC”替代选择性地降低了LUMO，导致HOMO-LUMO间隙大大减小。通过2,6 -二（喹啉- 8 -基）蒽的硼化反应，得到了一个更广泛的具有7个六元环的共轭体系（Qu - BEt）。氟化的py‐bpfs表现出特别有利的特性，包括相对较低的HOMO和LUMO水平，强烈的黄绿色荧光，有效的单线态氧敏化，同时抵抗自敏转化为其内过氧化物。
The functionalization of polycyclic aromatic hydrocarbons (PAHs) via B←N Lewis pair formation offers an opportunity to judiciously fine‐tune the structural features and optoelectronic properties, to suit the demands of applications in organic electronic devices, bioimaging, and as sensitizers for singlet oxygen generation. We demonstrate that the N‐directed electrophilic borylation of 2,6‐di(pyrid‐2‐yl)anthracene offers access to linearly extended acene derivativesPy‐BR(R=Et, Ph, C6F5). In comparison to indeno‐fused 9,10‐diphenylanthracene, the formal “BN for CC” replacement inPy‐BRselectively lowers the LUMO, resulting in a much reduced HOMO–LUMO gap. An even more extended conjugated system with seven six‐membered rings in a row (Qu‐BEt) is obtained by borylation of 2,6‐di(quinolin‐8‐yl)anthracene. FluorinatedPy‐BPfshows particularly advantageous properties, including relatively lower‐lying HOMO and LUMO levels, strong yellow‐green fluorescence, and effective singlet oxygen sensitization, while resisting self‐sensitized conversion to its endoperoxide.