Copper-Mediated Simple and Efficient Synthesis of Tribenzohexadehydro[12]annulene and Its Derivatives

Iyoda, Masahiko; Sirinintasak, Siriwan; Nishiyama, Yoshihiro; Vorasingha, Anusorn; Sultana, Fatema; Nakao, Kazumi; Kuwatani, Yoshiyuki; Matsuyama, Haruo; Yoshida, Masato; Miyake, Yoshihiro

doi:10.1055/s-2004-822393

Cited by 41 publications

(38 citation statements)

References 6 publications

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“…Synthesis and crystallization of the [12]DBAs: [12]DBA 2 was synthesized with a 71 % yield by the hydrolysis of the corresponding methyl ester 3, which is derived from the iod-ization of the diethyltriazene derivative 4 [23] with a 69 % yield and desilylation followed by modified Castro-Stephens cyclization [24] of the resultant iodoethynylbenzene derivative 6 with a 39 % yield in two steps, as shown in Scheme 1.…”

Section: Resultsmentioning

confidence: 99%

Superstructure‐Dependent Optical and Electrical Properties of an Unusual Face‐to‐Face, π‐Stacked, One‐Dimensional Assembly of Dehydrobenzo[12]annulene in the Crystalline State

Hisaki

Sakamoto

Shigemitsu

et al. 2008

Chemistry A European J

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To develop a novel pi-conjugated molecule-based supramolecular assembly, we designed and synthesized trisdehydrotribenzo[12]annulene ([12]DBA) derivative 2 with three carboxyl groups at the periphery. Recrystallization of 2 from DMSO gave a crystal of the solvate 23 DMSO. Crystallographic analysis revealed, to our surprise, that a face-to-face pi-stacked one-dimensional (1D) assembly of 2 was achieved and that the DMSO molecule played a significant role as a "structure-dominant element" in the crystal. This is the first example of [12]DBA to stack completely orthogonal to the columnar axis. To reveal its superstructure-dependent optical and electrical properties, 2 and its parent molecule 1, which crystallizes in a herringbone fashion, were subjected to fluorescence spectroscopic analysis and charge-carrier mobility measurements in crystalline states. The 1D stacked structure of 2 provides a red-shifted, broadened, weakened fluorescence profile (lambda(max) = 545 nm, phi(F) = 0.01), compared to 1 (lambda(max) = 491 nm, phi(F) = 0.12), due to strong interactions between the p orbitals of the stacked molecules. The charge-carrier mobility of the single crystal of 23 DMSO, as well as 1, was determined by flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements. The single crystal of 23 DMSO revealed significantly-anisotropic charge mobility (sigma(mu) = 1.5x10(-1) cm(2) V(-1) s(-1)) along the columnar axis (crystallographic c axis). This value is 12 times larger than that along the orthogonal axis (the a axis).

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Section: Resultsmentioning

confidence: 99%

Superstructure‐Dependent Optical and Electrical Properties of an Unusual Face‐to‐Face, π‐Stacked, One‐Dimensional Assembly of Dehydrobenzo[12]annulene in the Crystalline State

Hisaki

Sakamoto

Shigemitsu

et al. 2008

Chemistry A European J

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“…Iyoda et al synthesized octabutyl-substituted 65 b by copper-mediated cross-coupling in the presence of PPh 3 (1 %). [57] Compound 65 b exhibited a strong emission with F F = 0.21 and an associated Stokes shift of 190 nm. Diamond-shaped 66 and trefoil 67 also have a graphyne network ( Figure 10).…”

Section: Ortho-phenylene-ethynylene Macrocyclesmentioning

confidence: 99%

Conjugated Macrocycles: Concepts and Applications

2011

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One of the most important objectives in materials, chemical, and physical sciences is the creation of large conjugated macrocycles with well-defined shapes, since such molecules are not only theoretically and experimentally interesting but also have potential applications in nanotechnology. Fully unsaturated macrocycles are regarded as models for infinitely conjugated π systems with inner cavities, and exhibit unusual optical and magnetic behavior. Macrocycles have interior and exterior sites, and site-specific substitution at both or either site can afford attractive structures, such as 1D, 2D, and 3D supramolecular nanostructures. These nanostructures could be controlled through the use of π-extended large macrocycles by a bottom-up strategy. Numerous shape-persistent π-conjugated macrocycles have been synthesized, but only a few are on the nanoscale. This Review focuses on nanosized π-conjugated macrocycles (>1 nm diameter) and giant macrocycles (>2 nm diameter), and summarizes their syntheses and properties.

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“…Iyoda und Mitarbeiter synthetisierten die octabutylsubstituierte Verbindung 65 b durch eine kupfervermittelte Kreuzkupplung in Gegenwart von PPh 3 (1 %). [57] Die Verbindung 65 b wies eine starke Emission mit F F = 0.21 und eine damit verbundene Stokes-Verschiebung von 190 nm auf. Das rautenfçrmige 66 und das kleeblattfçr-mige 67 weisen ebenfalls ein Graphin-Netzwerk auf (Abbildung 10).…”

Section: Ortho-phenylenethinylen-makrocyclenunclassified

Konjugierte Makrocyclen: Konzepte und Anwendungen

2011

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Eines der wichtigsten Ziele in den Materialwissenschaften, der Chemie und der Physik ist die Herstellung von großen konjugierten Makrocyclen genau definierter Form, da solche Moleküle nicht nur theoretisch und experimentell interessant sind, sondern auch potenzielle Anwendungen in der Nanotechnologie haben. Vollständig ungesättigte Makrocyclen werden als Modelle für vollständig konjugierte π‐Systeme mit Hohlräumen herangezogen. Solche konjugierten π‐Systeme zeigen aufgrund ihrer cyclischen Konjugation ein ungewöhnliches optisches und magnetisches Verhalten. Makrocyclen haben nach innen und nach außen gerichtete Bindungsstellen, und eine positionsspezifische Substitution an beiden oder nur einer der beiden Bindungsstellen kann attraktive Strukturen zugänglich machen. Von besonderer Bedeutung sind ein‐, zwei‐ und dreidimensionale supramolekulare Nanostrukturen. Um die Bildung dieser Strukturen kontrollieren zu können, bietet sich die Bottom‐Up‐Synthese ausgehend von π‐expandierten Makrocyclen an. Zahlreiche formstabile π‐konjugierte Makrocyclen wurden synthetisiert, davon aber nur eine begrenzte Zahl an nanoskaligen Vertretern. In diesem Aufsatz konzentrieren wir uns auf nanometergroße π‐konjugierte Makrocyclen (>1 nm Durchmesser) sowie Riesenmakrocyclen (>2 nm Durchmesser) und fassen deren Synthesen und Eigenschaften zusammen.

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Copper-Mediated Simple and Efficient Synthesis of Tribenzohexadehydro[12]annulene and Its Derivatives

Cited by 41 publications

References 6 publications

Superstructure‐Dependent Optical and Electrical Properties of an Unusual Face‐to‐Face, π‐Stacked, One‐Dimensional Assembly of Dehydrobenzo[12]annulene in the Crystalline State

Superstructure‐Dependent Optical and Electrical Properties of an Unusual Face‐to‐Face, π‐Stacked, One‐Dimensional Assembly of Dehydrobenzo[12]annulene in the Crystalline State

Conjugated Macrocycles: Concepts and Applications

Konjugierte Makrocyclen: Konzepte und Anwendungen

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