Ring-expansion approach towards extended asymmetric benzopentafulvalenes: overcrowded olefinic structure and chain length-dependent properties,Organic Chemistry Frontiers

当前位置： X-MOL 学术 › Org. 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.)

Ring-expansion approach towards extended asymmetric benzopentafulvalenes: overcrowded olefinic structure and chain length-dependent properties
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2020-07-04 , DOI: 10.1039/d0qo00602e
Xinhao Wang _{1,

2,

3,

4} , Zihong Zhang _{1,

2,

3,

4} , Jing Guo _{2,

3,

4,

5,

6} , Chunyan Liu _{1,

2,

3,

4} , Yuanyuan Hu _{2,

3,

4,

5,

6} , Huiping Xiao _{4,

7,

8,

9} , Sheng Xie _{1,

2,

3,

4} , Jishan Wu _{10,

11,

12} , Zebing Zeng _{1,

2,

3,

4}

Affiliation

Creating π-extended benzopentafulvalenes can aid development of novel functional materials for organic electronics. Herein, we describe a facile ring-expansion strategy to allow precise construction of benzopentafulvalenes in an asymmetric benzoannulation mode, which provides an unprecedented opportunity to extend overcrowded olefins. This ring-expansion experienced sequenced skeletal rearrangement via a crucial spirobicyclic cation intermediate, rationalized by experiments and theoretical calculations. The resulting π-extended benzopentafulvalenes showed chain length-dependent physical properties. Substituent tuning led to available π-systems exhibiting LUMO energies comparable with those of fullerenes and stable ionic radicals upon one-electron oxidation/reduction. The π-extended nonplanar molecules displayed promising air-stable ambipolar semiconducting properties with balanced carrier-transport performances in thin film-fabricated OFETs. Our study provides insights into the fundamental relationships between molecular structures and optoelectronic properties for a new class of asymmetric benzopentafulvalenes.

中文翻译：

扩展不对称苯并五烯富勒烯的扩环方法：过度拥挤的烯烃结构和链长依赖性

生成π扩展的苯并五氟戊烯可以帮助开发用于有机电子的新型功能材料。在这里，我们描述了一种简便的扩环策略，可以在不对称的苯并环化模式下精确构建苯并五烯富戊烯，这为扩展拥挤的烯烃提供了前所未有的机会。这种扩环经历了通过通过实验和理论计算合理化的一种至关重要的螺双环阳离子中间体。所得的π-延伸的苯并五氟戊烯显示出链长依赖性的物理性质。取代基调谐导致可利用的π系统在单电子氧化/还原时表现出与富勒烯和稳定的离子自由基相当的LUMO能量。在薄膜制造的OFET中，π扩展的非平面分子显示出有希望的空气稳定的双极性半导体性质，并具有平衡的载流子传输性能。我们的研究为新型不对称苯并五富勒烯分子结构与光电性能之间的基本关系提供了见解。

更新日期：2020-08-14

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南