Chemical transformations of push-pull fluorenones: push-pull dibenzodicyanofulvenes as well as fluorenone- and dibenzodicyanofulvene-tetracyanobutadiene conjugates

被引：7

作者：

Kato, Shin-ichiro ^{[1
]}

Kijima, Tomokazu ^{[2
]}

Shiota, Yoshihito ^{[3
]}

Abe, Tsukasa ^{[3
]}

Kuwako, Satoshi ^{[2
]}

Miyauchi, Hidenori ^{[2
]}

Yoshikawa, Naoki ^{[2
]}

Yamamoto, Koji ^{[2
]}

Yoshizawa, Kazunari ^{[3
]}

Yoshihara, Toshitada ^{[2
]}

Tobita, Seiji ^{[2
]}

Nakamura, Yosuke ^{[2
]}

机构：

[1] Univ Shiga Prefecture, Sch Engn, Dept Mat Sci, 2500 Hassaka Cho, Hikone, Shiga 5228533, Japan

[2] Gunma Univ, Fac Sci & Technol, Div Mol Sci, 1-5-1 Tenjin Cho, Kiryu, Gunma 3768515, Japan

[3] Kyushu Univ, Inst Mat Chem & Engn, Nishi Ku, 744 Motooka, Fukuoka 8190395, Japan

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2020年 / 18卷 / 22期

关键词：

2+2 CYCLOADDITION; ELECTRONIC-PROPERTIES; STATE AROMATICITY; HIGHLY EFFICIENT; BUILDING-BLOCKS; SOLAR-CELLS; CHROMOPHORES; CYCLOPENTADIENONES; SEMICONDUCTORS; PHOTOPHYSICS;

D O I：

10.1039/c9ob02706h

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Push-pull fluorenones (FOs) were synthesized by treating a benzopentalenequinone (BPO) derivative with alkynes that bear an electron-rich aniline moiety via a regioselective [4 + 2] cycloaddition (CA) followed by a [4 + 1] retrocycloaddition (RCA). The resulting FOs were readily converted into dibenzodicyanofulvenes (DBDCFs) by treatment with malononitrile in the presence of TiCl4 and pyridine. The FOs and DBDCFs exhibit intramolecular charge-transfer (ICT) that manifests in absorptions at 350-650 nm and amphoteric electrochemical behavior. Furthermore, FOs and DBDCFs that contain a C C bond react with tetracyanoethylene in a formal [2 + 2] CA followed by a retro-electrocyclization to afford sterically congested tetracyanobutadiene (TCBD) conjugates. The substituent (H or Me) on the aromatic ring adjacent to the butadiene moiety thereby determines whether the butadiene adopts an s-cis or s-trans conformation, and thus controls the physicochemical properties of the resulting TCBDs. The TCBD conjugates exhibit ICT absorptions (<= 800 nm) together with up to four reversible reduction steps.

引用

页码：4198 / 4209

页数：12

共 64 条

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