Azatrioxa[8]circulenes: Planar Anti-Aromatic Cyclooctatetraenes

被引：80

作者：

Nielsen, Christian B. ^{[1
]}

Brock-Nannestad, Theis ^{[1
]}

Hammershoj, Peter ^{[1
]}

Reenberg, Theis K. ^{[1
]}

Schau-Magnussen, Magnus ^{[1
]}

Trpcevski, Denis ^{[1
]}

Hensel, Thomas ^{[1
]}

Salcedo, Roberto ^{[2
]}

Baryshnikov, Gleb V. ^{[3
]}

Minaev, Boris F. ^{[3
]}

Pittelkow, Michael ^{[1
]}

机构：

[1] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark

[2] Univ Nacl Autonoma Mexico, Inst Invest Mat, Coyoacan 04510, Mexico

[3] Bohdan Khmelnytsky Natl Univ, UA-18031 Cherkassy, Ukraine

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 12期

关键词：

aromaticity; fluorescence; heterocycles; polycycles; CYCLO-OLIGOMERIZATION; CONDENSATION PRODUCTS; COMPLEX OXIDATION; STRONG ACIDS; AROMATICITY; QUINONES; PHENOLS; SYSTEMS;

D O I：

10.1002/chem.201203113

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We describe herein the first synthesis of a new class of anti-aromatic planar cyclooctatetraenes: the azatrioxa[8]circulenes. This was achieved by treating a suitably functionalised 3,6-dihydroxycarbazole with 1,4-benzoquinones or a 1,4-naphthoquinone. We fully characterised the azatrioxa[8]circulenes by using optical, electrochemical and computational techniques as well as by single-crystal X-ray crystallography. The results of a computational study (NICS) suggest that the central planar cyclooctatetraene is anti-aromatic when the molecules are in neutral or oxidised states (2+), and that the corresponding dianions are aromatic. We discuss the aromatic/anti-aromatic nature of the planar cyclooctatetraenes and compare them with the isoelectronic tetraoxa[8]circulenes.

引用

页码：3898 / 3904

页数：7

共 44 条

[1]

[Anonymous], ASIAN CHEM LETT

[2]

Baryshnikov G. V., 2012, J MOL MODEL

[3]

BERG JE, 1977, TETRAHEDRON LETT, P1831

[4] Tetra-tert-butyltetraoxa[8]circulene and Its Unusual Aggregation Behaviour [J].

Brock-Nannestad, Theis ;

Nielsen, Christian B. ;

Schau-Magnussen, Magnus ;

Hammershoj, Peter ;

Reenberg, Theis K. ;

Petersen, Asger B. ;

Trpcevski, Denis ;

Pittelkow, Michael .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (31) :6320-6325

[5] Critical analysis of the local aromaticity concept in polyaromatic hydrocarbons [J].

Bultinck, Patrick .

FARADAY DISCUSSIONS, 2007, 135 :347-365

[6]

Burnett M.N., 1996, ORTEP-III: Oak Ridge Thermal Ellipsoid Plot Program for Crystal Structure Illustrations

[7] From thiophene to Sulflower [J].

Chernichenko, Konstantin Yu. ;

Balenkova, Elizabeth S. ;

Nenajdenko, Valentine G. .

MENDELEEV COMMUNICATIONS, 2008, 18 (04) :171-179

[8] Sulflower: A new form of carbon sulfide [J].

Chernichenko, Konstantin Yu. ;

Sumerin, Viktor V. ;

Shpanchenko, Roman V. ;

Balenkova, Elizabeth S. ;

Nenajdenko, Valentine G. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (44) :7367-7370

[9] Electron delocalization in various triply linked zinc(II) porphyrin arrays: role of antiaromatic junctions between aromatic porphyrins [J].

Cho, Sung ;

Yoon, Min-Chul ;

Kim, Kil Suk ;

Kim, Pyosang ;

Kim, Dongho .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2011, 13 (36) :16175-16181

[10] MP2 and DFT calculations on circulenes and an attempt to prepare the second lowest benzolog, [4]Circulene [J].

Christoph, Hilmar ;

Grunenberg, Joerg ;

Hopf, Henning ;

Dix, Ina ;

Jones, Peter G. ;

Scholtissek, Martin ;

Maier, Guenther .

CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (18) :5604-5616

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