Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel-Crafts/Bradsher Cyclization Reaction

被引：9

作者：

Balczewski, Piotr ^{[1
,2
]}

Kowalska, Emilia ^{[1
]}

Rozycka-Sokolowska, Ewa ^{[2
]}

Skalik, Joanna ^{[1
]}

Owsianik, Krzysztof ^{[1
]}

Koprowski, Marek ^{[1
]}

Marciniak, Bernard ^{[2
]}

Guziejewski, Dariusz ^{[3
]}

Ciesielskr, Witold ^{[3
]}

机构：

[1] Polish Acad Sci, Ctr Mol & Macromol Studies, Grp Funct Mat Synth, Div Organ Chem, Sienkiewicza 112, PL-90363 Lodz, Poland

[2] Jan Dlugosz Univ Czestochowa, Inst Chem Hlth & Food Sci, Fac Math & Nat Sci, Dept Mat & Struct Chem, Armii Krajowej 13-15, PL-42201 Czestochowa, Poland

[3] Univ Lodz, Dept Inorgan & Analyt Chem, Pomorska 163, PL-90236 Lodz, Poland

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2019年 / 25卷 / 62期

关键词：

acenes; aromatic substitution; cyclization; fluorescence; photostability; thermal stability; POLYCYCLIC AROMATIC-HYDROCARBONS; STACKED PACKING ARRANGEMENT; SINGLET MOLECULAR-OXYGEN; PENTACENE DERIVATIVES; TRANSISTOR PERFORMANCE; ENERGY-TRANSFER; ANTHRACENE; ACENES; PHOTOOXIDATION; OXIDATION;

D O I：

10.1002/chem.201903027

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T-decomp.=331-354 degrees C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 degrees C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60-70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel-Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S-1 state by molecular oxygen.

引用

页码：14148 / 14161

页数：14