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agoel13@yahoo.com; atul_goel@cdri.res.in
Received March 6, 2010
A novel series of thermally stable yellow light emitting fluoranthenes with an amine donor and a
nitrile acceptor was prepared from a ketene-S,S-acetal under mild conditions without using an
organometal catalyst. The organic light emitting device of yellow fluoranthene 10b exhibited
substantially low turn-on voltage (2.6 V) and maximum brightness of 470 Cd/m2 with luminance
efficiency of 2.0 Cd/A without using any dopant.
3656 J. Org. Chem. 2010, 75, 36563662 Published on Web 05/06/2010 DOI: 10.1021/jo100420x
r 2010 American Chemical Society
Goel et al.
JOC Article
Grignard reagents19 or Pd-catalyzed electrocyclic reaction
of a substituted acenaphthene.20
Recently we have shown that appropriately functionalized
donor-acceptor quateraryls21 and 9-unsubstituted fluor-
enes22a and fluorenones exhibited efficient, stable blue
emission and demonstrated their potential application in
developing blue OLEDs. We have demonstrated how the
positioning of donor-acceptor groups onto the fluorene-
fluorenone backbone transforms the green emission to blue
emission.22a To investigate photophysical properties of
fluoranthenes, a simple, general, and efficient synthetic route
that could offer flexibility of diverse functional groups in
their molecular framework was desirable. However, there is a
FIGURE 1. Fluorenes I-III and fluoranthenes IV-V. paucity of literature protocols that could generate fluor-
anthene derivatives with donor-acceptor and various chro-
Fluoranthenes possess interesting electronic and thermal mophoric functionalities in a rapid manner. Although
properties6 similar to those of fluorene with an advantage of numerous Diels-Alder reactions23 of 2H-pyran-2-ones with
having an oxidatively labile 9-methylene moiety of fluorene electron-deficient and electron-rich dienophiles do provide
blocked by a 1,9-fused benzene ring. Recent reports on fluor- annulated benzene derivatives, to the best of our knowledge,
anthene scaffold include fabrication of highly efficient blue none has utilized the chemistry of 2H-pyran-2-ones for
OLEDs,7,8 green OLEDs,9 and fluoranthene-based matrix preparing fluoranthene scaffold. On the basis of retro-synth-
material10 to improve charge-carrier transport. In this paper, esis, we envisaged that the reaction of 2H-pyran-2-ones (3
we report a highly rapid novel approach for the synthesis of and 9) with 2H-acenaphthylen-1-one (4) may furnish fluor-
thermally stable donor-acceptor fluoranthenes (V) and anthene derivatives under mild conditions.
their potential use in preparing economical, efficient non-
doped yellow-OLED devices. Results and Discussion
Few synthetic methodologies are available for the synth-
esis of fluoranthene derivatives, which mainly include the The reaction of methyl 2-carbomethoxy-3,3-bis(methyl-
cycloaddition reaction of cyclopentadienone derivatives and sulfanyl)acrylate22 1 with substituted acetophenones (2a-e)
alkynes or alkenes,11,12 Suzuki-Heck reaction of 1-bromo- under alkaline conditions furnished substituted 2H-pyran-2-
naphthalene and 2-bromophenyl boronic acid,13 reaction in- ones (3a-e) in excellent yields. Our approach to prepare
volving two triple bonds in 1,8-bis(phenylethynyl)naphtha- substituted fluoranthenes 5a-e involved stirring an equimo-
lene under thermal or photochemical conditions14 or in the lar mixture of 3a-e, 2H-acenaphthylen-1-one (4) in the
presence of metal catalysts15 such as RhCl3-Aliquat 336,16 presence of NaH, and dry THF at room temperature for
1,4-palladium migration from 2-iodo-1-phenylnaphtha- 35-90 min as shown in Scheme 1. The plausible reaction
lene,17 reaction of propargylic alcohol bearing a fluorene mechanism for the ring transformation of 2H-pyran-3-car-
moiety with diphenyl phosphine oxide,18 or benzoannula- boxylic acid methyl esters 3a-e into fluoranthenes 5a-e
tion reactions of R-oxoketene dithioacetals with various showed that the reaction is possibly initiated by Michael
addition of a conjugate base of 2H-acenaphthylen-1-one (4)
at position C6 of lactone 3, followed by intramolecular
(7) (a) Chiechi, R. C.; Tseng, R. J.; Marchioni, F.; Yang, Y.; Wudl, F.
Adv. Mater. 2006, 18, 325. (b) Suzuki, K.; Seno, A.; Tanabe, H.; Ueno, K.
cyclization involving the carbonyl functionality of 4 and
Synth. Met. 2004, 143, 89. C3 of the pyranone ring followed by elimination of carbon
(8) (a) Tseng, R. J.; Chiechi, R. C.; Wudl, F.; Yang, Y. Appl. Phys. Lett. dioxide to yield 5a-e.
2006, 88, 093512. (b) Tong, Q.-X.; Lai, S.-L.; Chan, M.-Y.; Zhou, Y.-C.;
Kwong, H.-L.; Lee, C.-S.; Lee, S.-T. Chem. Mater. 2008, 20, 6310. To demonstrate the synthetic utility and scope of this
(9) (a) Tong, Q.-X.; Lai, S.-L.; Chan, M.-Y.; Zhou, Y.-C.; Kwong, H.-L.; methodology for regiospecific introduction of electron donor
Lee, C.-S.; Lee, S.-T. Chem. Phys. Lett. 2008, 455, 79. (b) Tong, Q.-X.; Lai, or acceptor functionalities, we explored the synthesis of fluor-
S.-L.; Chan, M.-Y.; Lai, K.-H.; Tang, J.-X.; Kwong, H.-L.; Lee, C.-S.; Lee,
S.-T. Appl. Phys. Lett. 2007, 91, 153504. anthene derivatives with an amine donor and a nitrile acceptor
(10) Rosenow, T. C.; Walzer, K.; Leo, K. J. Appl. Phys. 2008, 103, substituent. An independent reaction of methyl 2-cyano-3,3-
043105.
(11) (a) Marcinow, Z.; Grove, D. I.; Rabideau, P. W. J. Org. Chem. 2002,
bis(dimethylsulfanyl)acrylate (6) with 1-acetylnaphthalene or
67, 3537. (b) Fabrizio, E. F.; Payne, A.; Westlund, N. E.; Bard, A. L.;
Magnus, P. P. J. Phys. Chem. A 2002, 106, 1961. (19) Panda, K.; Venkatesh, C.; Ila, H.; Junjappa, H. Eur. J. Org. Chem.
(12) (a) Viala, C.; Secchi, A.; Gourdon, A. Eur. J. Org. Chem. 2002, 4185. 2005, 2045.
(b) Wehmeier, M.; Wagner, M.; M ullen, K. Chem.;Eur. J. 2001, 7, 2197. (c) (20) (a) Fujiwara, M.; Ojima, I. In Modern Rhodium-Catalyzed Organic
Gourdon, A. Eur. J. Org. Chem. 1998, 2797. Reactions, Evans, P. A., Ed.; Wiley-VCH: Weinheim, Germany, 2005; p 129. (b)
(13) Wegner, H. A.; Scott, L. T.; de Meijere, A. J. Org. Chem. 2003, 68, Saito, S.; Yamamoto, Y. Chem. Rev. 2000, 100, 2901. (c) Jana, R.; Chatterjee, I.;
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Am. Chem. Soc. 1969, 91, 371. (b) Wu, Y.-T.; Hayama, T.; Baldridge, K. K.; Maulik, P. R.; Anand, R. S. Org. Lett. 2008, 10, 2553.
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FIGURE 5. Relative energy-level alignment and layer thickness of 10a-c OLEDs and actual device picture of fluoranthene 10b.
138.5, 138.8, 138.9, 139.6, 146.3, 169.1; HRMS calcd for Synthesis of 10-(Methylsulfanyl)-8-oxo-8H-7-oxa-fluoran-
C31H22O2S 458.1341, found 458.1337. thene-9-carbonitrile (11). A mixture of methyl 2-cyano-3,3-bis-
Synthesis of 10-(Naphthalen-1-yl)-8-(pyrrolidin-1-yl)fluoran- (methylsulfanyl)acrylate 6 (203 mg, 1 mmol, 1 equiv), 2H-acena-
thene-7-carbonitrile (10a). A mixture of 9a (316 mg, 1 mmol, phthylen-1-one 4 (168 mg, 1 mmol, 1 equiv), and NaH (60%
1 equiv), compound 4 (168 mg, 1 mmol, 1 equiv), and NaH (60% dispersion in oil, 48 mg, 1.2 mmol, 1.2 equiv) in dry THF (6 mL)
dispersion in oil, 60 mg, 1.5 mmol, 1.5 equiv) in dry THF (5 mL) was stirred at 0-5 C for 30-35 min. The progress of the reac-
was stirred at room temperature for 12 min. The progress of the tion was monitored by TLC and on completion solvent was eva-
reaction was monitored by TLC and on completion solvent was porated and the reaction mixture was poured onto crushed ice
evaporated and the reaction mixture was poured onto crushed with vigorous stirring. The precipitate obtained was filtered and
ice with vigorous stirring and finally neutralized with 10% HCl. purified on silica gel column with chloroform as the eluent to
The precipitate obtained was filtered and purified on a silica gel afford 203 mg (70%) of 11 as an orange solid. Rf 0.35
column with 30% chloroform in hexane as the eluent to afford (chloroform); mp 220-222 C; MS (EI) 291 (M); IR (KBr)
346 mg (82%) of 10a as a yellow solid. Rf 0.61 (1:1 chloroform- 2817, 2217, 1695, 1595, 1528 cm-1; 1H NMR (200 MHz, CDCl3)
hexane); mp 236-238 C; MS (ESI) 423 (M 1); IR (KBr) 3.14 (s, 3H), 7.67-7.79 (m, 2H), 7.94 (d, J = 8.3 Hz, 1H),
2924, 2199, 1632, 1580 cm-1; 1H NMR (300 MHz, CDCl3) 8.11-8.13 (m, 2H), 8.26 (d, J=7.08 Hz, 1H); HRMS calcd for
1.98-2.12 (m, 4H), 3.68-3.82 (m, 4H), 6.16 (d, J=7.0 Hz, 1H), C17H9NO2S 291.0354, found 291.0354.
6.61 (s, 1H), 7.02-7.09 (m, 1H), 7.27-7.33 (m, 1H), 7.45-7.71 Synthesis of 8-(Methylsulfany)acenaphtho[1,2-j]fluoranthene-
(m, 6H), 7.86 (d, J=8.1 Hz, 1H), 7.96-8.04 (m, 2H), 8.75 (d, J= 7-carbonitrile (12). A mixture of 11 (291 mg, 1 mmol, 1 equiv),
7.0 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) 25.8, 50.6, 89.1, compound 4 (168 mg, 1 mmol, 1 equiv), and NaH (60% dispersion
114.9, 120.3, 121.2, 123.9, 125.2, 125.5, 126.0, 126.1, 126.2, in oil 60 mg, 1.5 mmol, 1.5 equiv) in dry THF (6 mL) was stirred at
126.4, 127.4, 127.8, 127.9, 128.2, 128.4, 129.4, 131.4, 132.4, room temperature for 25 min. The progress of the reaction was
133.5, 134.7, 134.8, 137.9, 141.3, 143.5, 150.2; HRMS calcd monitored by TLC and on completion solvent was evaporated and
for C31H22N2 422.1783, found 422.1796. the reaction mixture was poured onto crushed ice with vigorous
Synthesis of 10-(Naphthalen-1-yl)-8-(piperidin-1-yl)fluoran- stirring and finally neutralized with 10% HCl. The precipitate
thene-7-carbonitrile (10b). A mixture of 9b (330 mg, 1 mmol, obtained was filtered and purified on a silica gel column with
1 equiv), compound 4 (168 mg, 1 mmol, 1 equiv), and NaH (60% 20% chloroform in hexane as the eluent to afford 214 mg (54%)
dispersion in oil, 60 mg, 1.5 mmol, 1.5 equiv) in dry THF (5 mL) of 12 as a yellow solid. Rf 0.71 (1:1 chloroform-hexane); mp >
was stirred at room temperature for 13 min. The progress of the 250 C; MS (ESI) 398 (M 1); IR (KBr) 2964, 2229, 1633, 1426
reaction was monitored by TLC and on completion solvent was cm-1; 1H NMR (300 Hz, CDCl3) 2.62 (s, 3H), 7.67-7.79 (m, 4H),
evaporated and the reaction mixture was poured onto crushed 7.89-7.99 (m, 4H), 8.55-8.61 (m, 2H), 8.65 (d, J=7.2 Hz, 1H),
ice with vigorous stirring and finally neutralized with 10% HCl. 8.95 (d, J=7.2 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) 19.9, 111.4,
The precipitate obtained was filtered and purified on a silica gel 117.9, 124.0, 125.2, 125.6, 126.2, 128.1, 128.3, 128.6, 128.7, 128.8,
column with 32% chloroform in hexane as the eluent to afford 129.1, 130.3, 133.6, 133.7, 133.9, 134.1, 134.6, 135.2, 135.8, 136.0,
370 mg (85%) of 10b as a yellow solid. Rf 0.62 (1:1 chloroform- 139.1, 141.9; HRMS calcd for C28H15NS 397.0925, found 397.0919.
hexane); mp 206-208 C; MS (ESI) 437 (M 1); IR (KBr) Experimental Device. Multilayer devices were fabricated to
2931, 2848, 2214, 1642, 1578 cm-1; 1H NMR (300 MHz, CDCl3) investigate the performance of yellow light-emitting materials
1.62-1.67 (m, 2H), 1.81-1.89 (m, 4H), 3.24-3.35 (m, 4H), (10a, 10b, and 10c) with the device configuration of ITO/
6.33 (d, J = 7.1 Hz, 1H), 6.95 (s, 1H), 7.10-7.15 (m, 1H), PEDOT:PSS (40 nm)/NPB(20 nm)/fluoranthenes (60 nm)/
7.26-7.34 (m, 1H), 7.48-7.76 (m, 6H), 7.91 (d, J = 8.1 Hz, BCP (8 nm)/Ca(3.2 nm)/Al (200 nm). The patterned ITO glass
1H), 7.98-8.05 (m, 2H), 8.70 (d, J=7.0 Hz, 1H); 13C NMR (75.5 plate was cleaned in 6:1:1 in RCA-I solution, rinsed in DI water
MHz, CDCl3) 24.1, 26.2, 53.8, 99.4, 117.8, 119.6, 122.4, 123.6, a number of times, and then dried. The ITO surface was treated
123.7, 125.5, 125.8, 126.1, 126.3, 126.5, 127.9, 128.0, 128.4, in ozone for 15 min. Immediately, the first layer of poly(3,4-
128.6, 128.7, 129.6, 131.3, 131.8, 132.8, 133.6, 134.1, 134.5, ethylenedioxythiophene) doped with poly(styrenesulfonic acid)
137.5, 141.1, 143.0, 156.3; HRMS calcd for C32H24N2 (PEDOT:PSS) was spin-coated on patterned ITO to form a hole
436.1940, found 436.1943. injection layer. The PEDOT-PSS was vacuum dried at 120 C
Synthesis of 8-(Piperidin-1-yl)-10-(pyren-1-yl)fluoranthene-7- for 1 h. All other organic layers and metal layers were sublimed
carbonitrile (10c). A mixture of 9c (406 mg, 1 mmol, 1 equiv), in high vacuum (1-5 10-6 mbar). Then devices were sealed
compound 4 (168 mg, 1 mmol, 1 equiv), and NaH (60% dis- with a covering glass plate with UV epoxy. The ILV characteri-
persion in oil, 60 mg, 1.5 mmol, 1.5 equiv) in dry THF (5 mL) stics of sealed OLED devices were obtained by using Keithley
was stirred at room temperature for 15 min. The progress of the source-measure unit. EL spectra were recorded with an optic
reaction was monitored by TLC and on completion solvent was spectrometer.
evaporated and the reaction mixture was poured onto crushed
ice with vigorous stirring and finally neutralized with 10% HCl. Acknowledgment. We gratefully acknowledge financial
The precipitate obtained was filtered and purified on a silica gel support by the Department of Science and Technology
column with 30% chloroform in hexane as the eluent to afford (DST), New Delhi, India. V.K. and S.C. are thankful to
420 mg (82%) of 10c as a yellow solid. Rf 0.62 (1:1 chloroform- UGC and CSIR, New Delhi for senior research fellowships.
hexane); mp >250 C; MS (ESI) 513 (M 1); IR (KBr) 2936, R.S.A. thanks the MHRD, New Delhi for financial support.
2850, 2215, 1632, 1581 cm-1; 1H NMR (300 MHz, CDCl3) The spectroscopic data provided by SAIF, CDRI is grate-
1.61-1.68 (m, 2H), 1.83-1.91 (m, 4H), 3.25-3.35 (m, 4H), 6.15 fully acknowledged. Authors are thankful to Dr. G. K. Jain
(d, J=7.1 Hz, 1H), 6.95-7.01 (m, 1H), 7.04 (s, 1H), 7.62 (d, J= and Dr. G. Palit, Scientist, CDRI for their support in
8.2 Hz, 1H), 7.71-7.77 (m, 1H), 7.84-7.93 (m, 3H), 8.03-8.28 obtaining absorbance and fluorescence data.
(m, 6H), 8.34 (d, J=7.8 Hz, 1H), 8.74 (d, J=7.1 Hz, 1H); 13C
NMR (75.5 MHz, CDCl3) 24.1, 26.2, 53.8, 99.4, 117.9, Supporting Information Available: 1H and 13C NMR spec-
120.0, 122.4, 123.7, 124.7, 124.8, 124.9, 125.0, 125.4, 125.5, tra, UV-vis and fluorescence spectra, DSC, TGA, cyclic vol-
126.2, 126.3, 126.7, 127.4, 127.9, 127.9, 128.0, 128.1, 128.7, tammograms and device efficiency graph for the compounds
129.6, 131.0, 131.4, 132.0, 132.8, 134.1, 134.5, 134.8, 141.5, 5a-e, 10a-c, 11, and 12. This material is available free of charge
143.1, 156.3. via the Internet at http://pubs.acs.org.