Alternating oligo(o,p-phenylenes) via ruthenium catalyzed diol-diene benzannulation: orthogonality to cross-coupling enables de novo nanographene and PAH construction.
Alternating oligo(o,p-phenylenes) via ruthenium catalyzed diol-diene benzannulation: orthogonality to cross-coupling enables de novo nanographene and PAH construction.
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DOI：
10.1039/c8sc03236j
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发表时间：
2018-10-28
期刊：
影响因子：
8.4
通讯作者：
Krische MJ
中科院分区：
文献类型：
--
作者：
Kasun ZA;Sato H;Nie J;Mori Y;Bender JA;Roberts ST;Krische MJ
钌 (0) 催化的二醇-二烯苯并环化能够形成对溴封端的交替低聚（邻,对亚苯基），并由此形成多种 PAH 材料。钌(0)催化的二醇-二烯苯并环化用于将低聚(对亚苯基亚乙烯基)2a–c、5和6转化为交替低聚(邻,对亚苯基)10a–c、11–13。相对于传统钯催化联芳交叉偶联的正交性允许构建对溴封端的交替低聚(邻,对亚苯基) 10b, 11-13，其可参与 Suzuki 交叉偶联和 Scholl 氧化。通过这种方式，制备了结构均质的纳米石墨烯 16a-f。纳米石墨烯 16a 包含 14 个稠合苯环，通过单晶 X 射线衍射进行了表征。以类似的方式，含有1,3,5-三取代苯核心的对溴封端的低聚(对亚苯基乙二醇)9被转化为可溶的、结构均质的六-近六苯并并苯18。制备了苯并噻吩封端的五聚体10c，并进行Scholl氧化以提供螺旋双(苯并噻吩)-稠合的五苯衍生物14。表征了纳米石墨烯 14、16a、b、d、e、h 和 18 的稳态吸收和发射特性。这些研究说明了钌(0)催化二醇-二烯苯并环化相对于经典联芳交叉偶联的正交性如何简化低聚亚苯基和纳米石墨烯的结构。
Ruthenium(0) catalyzed diol–diene benzannulation enables formation of p-bromo-terminated alternating oligo(o,p-phenylenes) and, therefrom, diverse PAH materials. Ruthenium(0) catalyzed diol–diene benzannulation is applied to the conversion of oligo(p-phenylene vinylenes) 2a–c, 5 and 6 to alternating oligo(o,p-phenylenes) 10a–c, 11–13. Orthogonality with respect to conventional palladium catalyzed biaryl cross-coupling permits construction of p-bromo-terminated alternating oligo(o,p-phenylenes) 10b, 11–13, which can be engaged in Suzuki cross-coupling and Scholl oxidation. In this way, structurally homogeneous nanographenes 16a–f are prepared. Nanographene 16a, which incorporates 14 fused benzene rings, was characterized by single crystal X-ray diffraction. In a similar fashion, p-bromo-terminated oligo(p-phenylene ethane diol) 9, which contains a 1,3,5-trisubstituted benzene core, is converted to the soluble, structurally homogeneous hexa-peri-hexabenzocoronene 18. A benzothiophene-terminated pentamer 10c was prepared and subjected to Scholl oxidation to furnish the helical bis(benzothiophene)-fused picene derivative 14. The steady-state absorption and emission properties of nanographenes 14, 16a,b,d,e,h and 18 were characterized. These studies illustrate how orthogonality of ruthenium(0) catalyzed diol–diene benzannulation with respect to classical biaryl cross-coupling streamlines oligophenylene and nanographene construction.
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影响因子：
2.8
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