Synlett 2016; 27(14): 2081-2084
DOI: 10.1055/s-0035-1561455
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© Georg Thieme Verlag Stuttgart · New York

Helically Twisted Tetracene: Synthesis, Crystal Structure, and Photophysical Properties of Hexabenzo[a,c,fg,j,l,op]tetracene

Yuuta Yano
a  Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
,
Hideto Ito
a  Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
,
Yasutomo Segawa
a  Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
b  JST, ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Nagoya 464-8602, Japan   Email: itami@chem.nagoya-u.ac.jp
,
Kenichiro Itami*
a  Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
b  JST, ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Nagoya 464-8602, Japan   Email: itami@chem.nagoya-u.ac.jp
c  Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Nagoya 464-8602, Japan
› Author Affiliations
Further Information

Publication History

Received: 25 March 2016

Accepted after revision: 25 April 2016

Publication Date:
17 May 2016 (online)

Abstract

The synthesis, X-ray crystal structure, and photophysical properties of unsubstituted hexabenzo[a,c,fg,j,l,op]tetracene are described. Unlike the previously reported tert-butyl-substituted analogues, unsubstituted hexabenzo[a,c,fg,j,l,op]tetracene showed a helically twisted conformation in the solid state. Density functional theory calculations on the possible conformers were also studied.

Supporting Information

 
  • References and Notes

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  • 7 Synthesis of Hexabenzo[a,c,fg,j,l,op]tetracene (1) To a 10 mL Schlenk tube containing a magnetic stirring bar were added pyrene (81.0 mg, 400 μmol), 5,5-dimethyldibenzo[b,d]silole (253 mg, 1.20 mmol), o-chloranil (394 mg, 1.60 mmol), and Pd(MeCN)4(BF4)2 (8.9 mg, 20 μmol). After dry DCE (4 mL) was added via a syringe through the septum, the septum was then replaced with argon-balloon-equipped condenser. The resultant mixture was stirred at reflux for 2.5 h. After the reaction mixture was cooled down to room temperature, this mixture was passed through a short pad of silica gel, washed with CH2Cl2, and solvents were removed under reduced pressure. The residue was subjected to silica gel chromatography (hexane–CH2Cl2, 10:1) to afford 1 (116 mg, 58%) as a white solid. 1H NMR (600 MHz, CD2Cl2): δ = 7.70 (t, J = 7.1 Hz, 4 H), 7.77 (t, J = 7.1 Hz, 4 H), 8.12 (t, J = 7.5 Hz, 2 H), 8.81 (d, J = 8.2 Hz, 4 H), 8.88 (d, J = 8.2 Hz, 4 H), 8.99 (d, J = 7.5 Hz, 4 H). 13C NMR (150 MHz, C2D2Cl4): δ = 123.6 (CH), 124.2 (Cq), 125.6 (CH), 125.8 (CH), 126.8 (CH), 127.0 (CH), 127.7 (Cq), 128.1 (Cq), 128.5 (CH), 129.3 (Cq), 130.8 (Cq). HRMS–FAB: m/z calcd for C40H22 [M]+: 502.1716; found: 502.1719; mp >300 °C. All other experimental procedures and characterization data of 1 can be found in the Supporting Information.
  • 8 Crystal Data of 1 Rigaku MicroMax007HF with PILATUS diffractometer, graphite-monochromated Mo Kα radiation (λ = 0.71075 Å), formula: C44H22, FW = 502.58, T = 123(2) K, monoclinic, P21/a, a = 7.839(4) Å, b = 26.538(11) Å, c = 11.640(5) Å, β = 98.627(12)°, V = 2394.1(19) Å3, Z = 4, D calc = 1.394 g/cm3, μ = 0.079 mm–1, F(000) = 1048, crystal size: 0.20 × 0.20 × 0.01 mm3, θ range: 3.04–25.00°, reflections collected: 29984, independent reflections: 4172, R int = 0.0760, param.: 361, GOF on F 2: 1.121, R 1 = 0.0832, wR 2 = 0.2285 (I > 2σ(I)), R 1 = 0.1036, wR 2 = 0.2634 (all data) The structures were solved by direct methods with SIR-97 and refined by full-matrix least-squares techniques against F 2 (SHELXL-97). The intensities were corrected for Lorentz and polarization effects. The nonhydrogen atoms were refined anisotropically. Hydrogen atoms were placed using AFIX instructions. CCDC 1450739 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
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