Diazapentacene Derivatives: Synthesis, Properties, and ... · Wenǂ, Iryna Lebedyeva ... Cyclic...
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Diazapentacene Derivatives: Synthesis, Properties, and Structures. John J. Hoff † , Lei Zhu ǂ , Yutong Dong † , Thomas Albers † , Peter J. Steel § , Xianwei Cui ǂ , Ying Wen ǂ , Iryna Lebedyeva † , and Shaobin Miao *† † Department of Chemistry and Physics, Augusta University, 1120 15th St., Augusta, GA 30912, USA * Corresponding author. E-mail: [email protected] ǂ College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P.R. China § Chemistry Department, University of Canterbury, Christchurch, 8140, New Zealand Synthesis All reagents and solvents were obtained from commercial suppliers and used without further purification except for tetrahydrofuran (THF) that had been distilled over sodium/benzophenone. 1,4-Bis((triisopropylsilyl)ethynyl)anthracene-2,3-diamine (1) 1,2 was synthesized according to the literature. 1 H-NMR (300 MHz) and 13 C-NMR (75 MHz) spectra were recorded on a Bruker DRX-300 spectrometer at room temperature. Infrared spectra were recorded on a Thermo Scientific Nicolet iS5 FT-IR spectrometer with ATR accessory. Absorption spectra were recorded on a Hitachi U-4100. Emission spectra were recorded on a Hitachi F-7000 fluorescence spectrophotometer. High resolution mass spectrometry were recorded on a MAT 95 XP mass spectrometer. Melting points were determined with a melting point apparatus MEL-TEMP (Thermo Scientific) and are uncorrected. X-ray intensity data were collected at 120(10) K using a SuperNova, Dual, Cu at zero, Atlas diffractometer (Cu Ka radiation, λ = 1.54184 Å). Cyclic voltammetry (CV) measurements were carried out on a CHI 760E Electrochemical workstation (Shanghai, China). NH 2 NH 2 1 X X N N X X O O 2, X = CH 3, X = N Si Si Si Si Synthesis of 2: To the mixture of 1 (0.500 g, 0.879 mmol) in CH 3 COOH (20.0 mL) was added phenanthrene-9,10-dione (0.201 g, 0.965 mmol, 1.10 equivalent) at r.t. The resultant mixture was Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2016
Transcript of Diazapentacene Derivatives: Synthesis, Properties, and ... · Wenǂ, Iryna Lebedyeva ... Cyclic...
Diazapentacene Derivatives: Synthesis, Properties, and Structures.
John J. Hoff †, Lei Zhuǂ, Yutong Dong†, Thomas Albers†, Peter J. Steel§, Xianwei Cuiǂ, Ying Wenǂ, Iryna Lebedyeva†, and Shaobin Miao*†
† Department of Chemistry and Physics, Augusta University, 1120 15th St., Augusta, GA 30912, USA
* Corresponding author. E-mail: [email protected]
ǂ College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P.R. China
§ Chemistry Department, University of Canterbury, Christchurch, 8140, New Zealand
Synthesis
All reagents and solvents were obtained from commercial suppliers and used without further purification except for tetrahydrofuran (THF) that had been distilled over sodium/benzophenone. 1,4-Bis((triisopropylsilyl)ethynyl)anthracene-2,3-diamine (1) 1,2 was synthesized according to the literature. 1H-NMR (300 MHz) and 13C-NMR (75 MHz) spectra were recorded on a Bruker DRX-300 spectrometer at room temperature. Infrared spectra were recorded on a Thermo Scientific Nicolet iS5 FT-IR spectrometer with ATR accessory. Absorption spectra were recorded on a Hitachi U-4100. Emission spectra were recorded on a Hitachi F-7000 fluorescence spectrophotometer. High resolution mass spectrometry were recorded on a MAT 95 XP mass spectrometer. Melting points were determined with a melting point apparatus MEL-TEMP (Thermo Scientific) and are uncorrected. X-ray intensity data were collected at 120(10) K using a SuperNova, Dual, Cu at zero, Atlas diffractometer (Cu Ka radiation, λ = 1.54184 Å). Cyclic voltammetry (CV) measurements were carried out on a CHI 760E Electrochemical workstation (Shanghai, China).
NH2
NH2
1
X
X
N
N X
X
O
O
2, X = CH3, X = N
Si
Si
Si
Si
Synthesis of 2: To the mixture of 1 (0.500 g, 0.879 mmol) in CH3COOH (20.0 mL) was added phenanthrene-9,10-dione (0.201 g, 0.965 mmol, 1.10 equivalent) at r.t. The resultant mixture was
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
heated at 100 °C for 2.5 hours. The mixture was cooled down to r.t. and was added to 200 mL of H2O. The mixture was then filtered and the precipitate was washed with H2O (3x200mL), CH3OH (3x100mL), and dried. The dark-green product 2 (0.321g, 49%) was obtained after column chromatography on silica gel using a Hex:CH2Cl2 (5:1, v/v) solvent mixture. m. p. = 342-344 °C. IR (ATR): 2939, 2889, 2862, 2134, 1602, 1449, 1354 cm-1. 1H-NMR (300 MHz, CDCl3): δ = 9.59-9.56 (dd, J = 8.0 Hz, J = 1.4 Hz, 2H), 9.49 (s, 2H), 8.50-8.48 (d, J = 8.0 Hz, 2H), 8.10-8.07 (dd, J = 6.5 Hz, J = 3.2 Hz, 2H), 7.81-7.78 (dt, J = 7.2 Hz, J = 1.4 Hz, 2H), 7.72-7.69 (t, J = 7.2 Hz, 2H), 7.56-7.53 (dd, J = 6.6 Hz, J = 3.2 Hz, 2H), 1.45-1.42 ppm (m, 42H). 13C-NMR (75 MHz, CDCl3): δ = 144.21, 139.97, 132.81, 132.72, 132.21, 131.18, 130.59, 128.66, 127.96, 127.44, 126.78, 126.58, 123.01, 120.44, 107.92, 103.68, 19.01, 11.80 ppm. HRMS (EI, 70ev): m/z [M]+ calcd for C50H56N2Si2: 740.3977u, found: 740.3960u.
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
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3
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7.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.29.39.49.59.6f1 (ppm)
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Figure S1. 1H-NMR (300 MHz) spectrum of 2 in CDCl3 at 300 K.
101520253035404550556065707580859095100105110115120125130135140145f1 (ppm)
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Figure S2. 13C-NMR (75 MHz) spectrum of 2 in CDCl3 at 300 K.
Synthesis of 3: To the mixture of 1 (0.500 g, 0.879 mmol) in CH3COOH (25.0 mL) was added 1,10-phenanthroline-5,6-dione (0.203 g, 0.966 mmol, 1.10 equivalent) at r.t. The resultant mixture was heated at 100 °C for 2.5 hours. The mixture was cooled down to r.t. and was added to 200 mL of H2O. The mixture was then filtered and the precipitate was washed with H2O (3x200mL), CH3OH (3x100mL), and dried. The dark-green product 3 (0.430g, 66%) was obtained after column chromatography on silica gel using a CH2Cl2:ethyl acetate (1:1, v/v) solvent mixture. m. p. = 350-352 °C. IR (ATR): 2941, 2863, 2128, 1587, 1460, 1354 cm-1. 1H-NMR (300 MHz, CDCl3): δ = 9.78-9.75 (dd, J = 8.1 Hz, J = 1.8 Hz, 2H), 9.51 (s, 2H), 9.26-9.24 (dd, J = 4.5 Hz, J = 1.8 Hz, 2H), 8.11-8.07 (dd, J = 6.5 Hz, J = 3.3 Hz, 2H), 7.77-7.73 (dd, J = 8.1 Hz, J = 4.5 Hz, 2H), 7.58-7.55 (dd, J = 6.7 Hz, J = 3.3 Hz, 2H), 1.44-1.42 ppm (m, 42H). 13C-NMR (75 MHz, CDCl3): δ = 153.07, 149.37, 142.70, 139.76, 134.47, 133.04, 132.40, 128.67, 128.00, 126.99, 124.20, 120.98, 108.81, 103.31, 19.00, 11.75 ppm. HRMS (EI, 70ev): m/z [M]+ calcd for C48H54N4Si2: 742.3882u, found: 742.3895u.
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
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Figure S3. 1H-NMR (300 MHz) spectrum of 3 in CDCl3 at 300 K.
101520253035404550556065707580859095105115125135145155f1 (ppm)
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Figure S4. 13C-NMR (75 MHz) spectrum of 3 in CDCl3 at 300 K.
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E(V) vs SCE
I(μA
)
Figure S5. Cyclic voltammetry of 2 and 3 (0.4×10-3 M) on a glassy carbon electrode in CH2Cl2 + 0.1 M nBu4NBF4 at room temperature, scan at v = 200 mV/s. A glassy carbon electrode as the working electrode, a Pt wire as a counter electrode and a saturated calomel electrode (SCE) as a reference.
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Figure S6. Normalized UV-vis absorption spectra of 2 in different solvents.
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Figure S7. Normalized emission spectra of 2 in different solvents (excitation wavelength: 590nm).
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Figure S8. Normalized UV-vis absorption spectra of 3 in different solvents.
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nsity
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.
Figure S9. Normalized emission spectra of 3 in different solvents (excitation wavelength: 600nm).
References:
1. Appleton, A. L.; Brombosz, S. M.; Bralow, S.; Sears, J. S.; Bredas, J.-L.; Marder, S. R.; Bunz, U. H. F. Nat. Commun. 2010, 1, 91.
2. Appleton, A. L.; Miao, S.; Brombosz, S. M.; Berger, N. J.; Barlow, S.; Marder, S. R.; Lawrence, B. M.; Hardcastle, K. I.; Bunz, U. H. F. Org. Lett. 2009, 11, 5222-5225.
