Two novel thiaheterohelicene derivatives were synthesized from the corresponding 2,2'-(2,6-naphthalenediyl-di-2,1-ethenediyl) bis-thiophene and its dimethyl substituted analogue 2,2'-(2,6-naphthalenediyldi-2,1-ethenediyl) bis-2’’-methylthiophene using oxidative photo cyclization reaction. The compounds were characterized by 1H NMR, electron impact-mass spectrometry, elemental analyses, and the absolute molecular structures were determined by single crystal X-ray diffraction analysis. They crystallized under monoclinic system with space group P2 1/n for the unsubstituted compound and P2 1/c for the methyl substituted compound, respectively. The dihedral angle between the terminal thiophene ring and the molecular center was observed to be 20.82 ? for the unsubstituted compound and 14.27 ? for the methyl substituted compound, respectively. Furthermore, molecules oriented as herringbone structures by intermolecular π-π stacking in the crystals. The relative study of the actual arrangement of these molecules has been carried out using X-ray diffraction analysis. The two molecules have different crystal packing. The molecule 3b has herring bone like arrangement due to the substituent bulkiness and weak CH-π interaction. On the other hand, the molecular packing of molecule 3a is not herringbone probably due to the multiple weak intermolecular CH-S short contacts between columns consisting of stacked molecules.
Helicenes are ortho fused polycyclic aromatic compounds. They have attracted great attention of researchers because of the unique properties associated with their structure. Helicenes have found many applications in various fields such as organic electronic materials [
All reagents and solvents were purchased from commercial sources and are used without further purification. The 1H-NMR spectrum was recorded on a JEOL JNM A-500 spectrometer in CDCl3 with tetramethylsilane (Me4Si) as the internal reference. The electron impact (EI) mass spectrum (MS) of the compound was obtained on a JEOL JMS-SX102A spectrometer using dichloromethane (DCM) as the solvent. The instrument was operated in positive ion mode over an m/z range of 100 - 1200. Elemental analysis was performed on a YANAKO MT-5 CHN analyzer.
Typical procedure for the synthesis of the compounds 2a and 2b.
2,6-Bis(triphenylphosphinnomethyl)-naphthalene dichloride Wittig Salt (0.75 g, 1.0 mmol) 1 was dissolved in 200 ml of dry THF in round bottom flask under argon stream. To this thiophene carboxaldehydes (2.0 mmol) was added dropwise, the mixture was stirred for 14 h, quenched with 1.0% HCl aq., and extracted twice with CH2Cl2. The organic layers were washed once with 50 mL water, twice with 50 mL of brine solution, dried over MgSO4, and the solvent was removed under reduced pressure. The precursor 2a and 2b were obtained using silica gel (Wako gel C-300) column chromatography (280 mg, 82% yield for 2a, 270 mg, 72% for 2b) with CH2Cl2 as an eluent.
2a1H NMR (400 MHz, CDCl3): 7.04 (d, 2H, J = 8.0 Hz, ethenyl H), 7.05 (d, 2H, J = 7.0 Hz, aryl H), 7.12 (s, 2H,aryl H), 7.22 (d, 2H, J = 7.0 Hz, aryl H), 7.36 (d, 2H, J = 8.0 Hz, ethenyl H), 7.67 (d, 4H, J = 6.6 Hz, aryl H), 7.78 (t, 2H, J = 6.6 Hz, aryl H); EI-MS: m/z 344 (M+).
2b1H NMR (400 MHz, CDCl3):2.50 (6H, s, CH3), 6.66 (d, 2H, J = 7.7 Hz, ethenyl H), 6.90 (d, 2 H, J = 7.7 Hz, ethenyl H), 6.95 (d, 2H, J = 7.4 Hz, aryl H), 7.25 (d, 2H, J = 7.4 Hz, aryl H), 7.63 (d, 2 H, J = 7.2 Hz, aryl H), 7.74 (s, 2H, aryl H), 7.75 (d, 2H, J = 7.2 Hz, aryl H); EI-MS: m/z 372 (M+).
Typical procedure for the Photo cyclization of the compounds 2a and 2b.
4,9-Bis{2’-(2”-substituted thiophenyl)ethenyl}-naphthalene (1.0 mmol) 2 was dissolved in 200 ml of benzene in round bottom flask. To this iodine(10 mmol) was added, the mixture was stirred and irradiated UV light using high-pressure Hg lump for 14 h, quenched with 1.0 mol/L Na2S2O3 solution, allowed to warm to room temperature, and extracted twice with AcOEt. The organic layers were washed once with 50 mL water, twice with 50 mL of brine solution, dried over MgSO4, and the solvent was removed under reduced pressure. The title compound was obtained using silica gel (Wako gel C-300) column chromatography (190 mg, 56% yield for 3a, 120 mg, 33% for 3b) with CH2Cl2 as an eluent.
3a M.p.: 226˚C - 232˚C; 1H NMR (400 MHz, CDCl3): 7.68 (d, 2H, J = 7.3 Hz, aryl H), 7.87 (d, 2 H, J = 7.5 Hz, aryl H), 8.02 (d, 2H, J = 7.2 Hz, aryl H), 8.05 (d, 2H, J = 7.3 Hz, aryl H), 8.54 (d, 2H, J = 7.2 Hz, aryl H), 9.04 (d, 2 H, J = 7.5 Hz, aryl H); EI-MS: m/z 340 (M+); Analysis: C22H12S2, Found: C: 77.74%, H: 3.61%, Calculated: C: 77.61%, H: 3.55%).
3b M.p.: 232˚C - 236˚C; 1H NMR (400 MHz, CDCl3): 2.80 (s, 6H, CH3), 7.85 (d, 2H, J = 7.3 Hz, aryl H), 8.00 (d, 2 H, J = 7.3 Hz, aryl H), 8.04 (d, 2H, J = 7.4 Hz, aryl H), 8.26 (s, 2H, aryl H), 9.06 (d, 2 H, J = 7.4 Hz, aryl H); EI-MS: m/z 368 (M+); Analysis: C24H16S2, Found: C: 78.34%, H: 4.49%, Calculated: C: 78.22%, H: 4.38%).
Single crystals of two compounds 3a and 3b were obtained at room temperature from a solution of dichloromethane/n-hexane (v/v = 1/1).
The crystal data were recorded on a Bruker APEX II KY CCD diffractometer equipped with graphite monochromatized (doubly curved silicon crystal) Mo-Kα-radiation (λ = 0.71073 Å) from a sealed micro focus tube, and a nominal crystal to area detector distance of 58 mm. X-ray generator settings were 50 kV and 30 mA. The data were collected at −183˚C (90 K). Data were acquired using four sets of Omega scans at different Phi settings and the frame width was 0.5˚. APEX2 software was used for the preliminary determination of the unit cell [
The average residual for symmetry equivalent reflections were Rint = 4.13% with Rσ = 3.62% for 3a and Rint = 4.81% with Rσ = 3.85% for 3b, respectively. XPREP [
Several scans in the ω direction were made to increase the number of redundant reflections, which were averaged in the refinement cycles. This procedure replaces an empirical absorption correction [
Hydrogen atoms at carbon atoms were added geometrically and refined using a riding model (constrained), whereas the hydrogen atoms at carbon atoms were exact localized and refined isotropically with bond restraints of 89 pm for C-H. All non-hydrogen atoms were refined with anisotropic displacement parameters.
Synthetically, the two desired compounds 3a and 3b were obtained in 70 % isolated yield from the corresponding precursors bis(substituted-thienylethenyl) naphthalenes 2a and 2b by oxidative photo cyclization reaction in the presence of iodine as an oxidative reagent (Scheme 1). Structural properties in solution are in line with expectations, as shown by NMR spectroscopy. For the compounds 3a and 3b, the four protons (Ha and Hb), which located in Fjord regions were observed at low magnetic field region. The NMR shift values are 8.54 ppm and 9.04 ppm for 3a, 8.26 ppm and 9.06 ppm for 3b, respectively. The shifts were well explained by the strong ring current effects of the π-systems on the molecules.
The exact molecular structures of the compounds 3a and 3b are determined by using X-ray diffraction analysis (
Scheme 1. Synthesis of the title compounds 3a and 3b.
molecules in the unit cell (
Furthermore, the molecular packing of the compound 3a and 3b in the crystals were quite different. The packing of 3b is called “Herring-Bone” structure. In general, almost organic semiconductive compounds consisting of polynuclear aromatic hydrocarbons and polynuclear heteroaromatics usually form two-dimensional herringbone molecular orientation in crystal. On the contrary, packing style of 3a is not “Herring-Bone” structure. Difference between crystal packing of 3a and 3b, is probably due to the substituent bulkiness and weak CH-π interaction. In the crystal of 3a, multiple weak intermolecular CH-S short contacts are existed between columns consisting of stacked molecules (
HOMO and LUMO energy level calculations of the π systems of the compounds were carried out using density functional theory (DFT) B3-LYP 6-31G(d) level on SPARTAN14 Suite program [
Empirical Formula Formula Weight Temperature Crystal size Crystal color Crystal system Space group a b c β Limiting indices Volume Z Calculated density Reflection collected/unique θ range for data collection data completeness Absorption coefficient F(000) Absorption correction Refinement method Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I > 2sigma(I)] wR2 indices (all data) Largest diff. peak and hole (eÅ−3) | C22H12S2 340.44 90 K 0.30 × 0.20 × 0.15 mm Yellow Monoclinic P21/n(No. 14) a = 13.873(4)Å b = 3.8474(11)Å c = 27.800(8)Å 90.605 (3)˚ −17 ≤ h ≤ 18, −5 ≤ k ≤ 5, −36 ≤ l ≤ 35 1483.7(7)Å3 4 1.524 g/cm−1 15805/3572 [R(int) = 0.0413] θmax = 28.67˚, θmin = 1.47˚ 93.6% 0.357 mm−1 704 Empirical Full-matrix LS on F2 3572/0/217 1.048 R1 = 0.0399 wR2 = 0.1037 0.407 and −0.333 | C24H16S2 368.49 90 K 0.20 × 0.15 × 0.10 mm Yellow Monoclinic P21/c (No. 14) a = 5.5102(15)Å b = 6.5517(18)Å c = 22.431(6)Å 98.727(9)˚ −17 ≤ h ≤ 18, −5 ≤ k ≤ 5, −36 ≤ l ≤ 35 809.2(4) Å3 2 1.512 g/cm−1 7585/1513 [R(int) = 0.0481] θmax = 25.55˚, θmin = 1.82˚ 99.7% 0.334 mm−1 384 Empirical Full-matrix LS on F2 1513/0/119 1.160 R1 = 0.0495 wR2 = 0.1195 0.347 and −0.286 |
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On the other hand, we also performed molecular calculations of these compounds 3a and 3b to compare with X-ray results (
From the calculated results, we also obtained HOMO and LUMO energy levels, HOMO −5.44 eV LUMO −1.36 eV for 3a and HOMO −5.20 eV LUMO 1.33 eV for 3b, respectively. The values are slightly different from those of the molecules in crystals, and these differences are probably due to the molecular structures. From the results the compounds 3a and 3b are seems to be good p-type semiconducting materials.
Furthermore, UV visible and fluorescence spectra were acquired to determine the photochemical properties of the two compounds 3a and 3b. The strong emissions were observed for the compounds 3a and 3b in chloroform and the peak maxima are detected at 405 nm for 3a and 403 nm for 3b, respectively. The strong emissions can be explained by the molecular shapes of the compounds 3a and 3b. In another words, the compounds have no flexible parts, therefore, the excited energy cannot be relaxed through molecular vibrations.
The novel air stable thiaheterohelicene derivatives were prepared in high yield and characterized by 1H NMR, elemental analyses and electron impact-mass spectrometry. The exact molecular structures and the molecular packing of the compounds were confirmed by single crystal X-ray analyses. The crystal packing was the same styles as other semiconductor compounds. Therefore, the semiconducting properties of these compounds are under investigation now.
We are grateful to the Center for Instrumental Analysis, Kyushu Institute of Technology (KITCIA), for elemental analyses, mass spectra and 1NMR spectra, and X-ray analyses. We also thank Dr. Kenji Yoza (Bruker AXS JAPAN) for experimental assistance during the refinements of the X-ray analyses. This research was financially supported by Kitakyushu Foundation for the Advancement of Industry Science and Technology (FAIS) and JSPS KAKENHI Grant Number 15K05611.
Moriguchi, T., Mitsumoto, K., Nishizawa, Y., Yakeya, D., Jalli, V. and Tsuge, A. (2016) Syntheses, Characterization and DFT Analysis of Two Novel Thiaheterohelicene Derivatives. Crystal Structure Theory and Applications, 5, 63-73. http://dx.doi.org/10.4236/csta.2016.54006
CCDC no. 1010570 for the compound 3a and 1010571 for the compound 3b contain the supplementary crystallographic data. The data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallography Data Centre, 12 Union Road, Cambridge, CB2 IEZ, UK. Fax: +44(0) 1223-336033.
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