Alternating oligo(o, p-phenylenes) via ruthenium catalyzed diol-diene benzannulation: orthogonality to cross-coupling enables de novo nanographene and PAH construction

被引：11

作者：

Kasun, Zachary A. ^{[1
]}

Sato, Hiroki ^{[1
]}

Nie, Jing ^{[1
]}

Mori, Yasuyuki ^{[1
]}

Bender, Jon A. ^{[1
]}

Roberts, Sean T. ^{[1
]}

Krische, Michael J. ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA

来源：

CHEMICAL SCIENCE | 2018年 / 9卷 / 40期

关键词：

POLYCYCLIC AROMATIC-HYDROCARBONS; HEXA-PERI-HEXABENZOCORONENES; BENZENE CARBON NANOCAGES; CIRCULAR-DICHROISM; BUILDING-BLOCKS; SCHOLL REACTION; OPTICAL-PROPERTIES; 4+2 CYCLOADDITION; CRYSTAL-STRUCTURE; ORTHO-PHENYLENES;

D O I：

10.1039/c8sc03236j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：7866 / 7873

页数：8