Supporting Information
Effective Tuning of Ketocyanine Derivatives through Acceptor
Substitution
Ambata Poe, Andrea Della Pelle, Sean Byrnes, and S. Thayumanavan*[a]
chem_201406625_sm_miscellaneous_information.pdf
General methods. All reagents were purchased from commercial sources and used as received,
unless otherwise mentioned. 3,6-dibromophenanthrene-9,10-dione and 3,6-dibromo-9H-fluoren9-one were synthesized according to previously reported procedures.
[1] 1
H NMR spectra were
recorded on a 400 MHz Bruker NMR spectrometer and recorded in ppm using the residual
solvent peak as the internal standard (CDCl3 at 7.26 ppm; acetone-d6 at 2.05 ppm). When peak
multiplicities are given, the following abbreviations are used: s, singlet; d, doublet; dd, doublet of
doublets t, triplet; m, multiplet.
13
C NMR spectra were proton decoupled and recorded on a 100
MHz Bruker NMR spectrometer using the carbon signal of the deuterated solvent as the internal
standard (CDCl3 at 77.16 ppm; acetone-d6 at 206.68 ppm). Solution absorbance spectra were
recorded on a Cary 100 spectrophotometer in dichloromethane. All extinction coefficients were
determined from a linear fit of five data points.
Detailed synthetic methods.
Synthesis of 3,6-bis(diphenylamino)-9H-fluoren-9-one (DAA-Fl).
Pd2dba3 (0.27 g, 0.3
mmol), P(tBu)3HBF4 (0.17 g, 0.6 mmol), and NaOtBu (1.7 g, 17.7 mmol) was suspended in 25 mL
degassed toluene and stirred at room temperature for 10 mins. Diphenylamine (2.3 g, 13.6
mmol) and 3,6-dibromo-9H-fluoren-9-one (2.0 g, 5.9 mmol) was added and the reaction was
refluxed overnight. The toluene was removed under vacuum and the crude product was purified
1
on CombiFlash (22%). H NMR (400MHz, acetone-d6): δ 7.43 (d, 2H, J = 8 Hz), 7.35 (t, 8H, J = 8
Hz), 7.15 (m, 12H, J = 8 Hz), 7.12 (d, 2H, J = 2 Hz), 6.75 (dd, 2H, J = 8Hz).
13
C NMR (100MHz,
CDCl3): δ 191.0, 162.0, 153.5, 146.8, 145.3, 129.8, 129.7, 128.6, 126.1, 125.7, 125.2, 124.8,
124.5, 122.4, 121.4, 115.2, 113.4, 29.1. m/z calculated for C37H26N2O: 514.2 found by FAB:
515.4.
Synthesis of 2-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)malononitrile (DAA-Fl-CN).
DAA-Fl (100 mg, 0.2 mmol) and malononitrile (39 mg, 0.59 mmol) were dissolved in 15 mL
chloroform. Piperidine (0.12 mL, 1.17 mmol) was added and the reaction was refluxed overnight.
The solvents were removed under vacuum and the crude mixture was purified by Combiflash
1
(10%). H NMR (400MHz, CDCl3): δ 8.14 (d, 2H, J = 8 Hz), 7.31 (t, 8H, J = 8 Hz), 7.14 (m, 12H),
6.96 (d, 2H, J = 4 Hz), 6.73 (dd, 2H, J = 8 Hz).
13
C NMR (100MHz, CDCl3): δ 153.3, 146.2,
1 143.5, 129.9, 128.0, 127.7, 126.2, 125.3, 120.2, 115.3, 112.6, 1.2. m/z calculated for C40H26N4:
562.2 found by FAB: 562.4.
Synthesis
of
5-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-1,3-dimethylpyrimidine-
2,4,6(1H,3H,5H)-trione (DAA-Fl-6O). DAA-Fl (50 mg, 0.1 mmol) and 1,3-dimethylbarbituric acid
(47 mg, 0.3 mmol) were dissolved in 2 mL acetic acid and 2 mL acetic anhydride and refluxed
overnight. The acetic acid and acetic anhydride were removed under vacuum and the crude
mixture was dissolved in DCM and washed twice with water and once with saturated sodium
bicarbonate. The product was purified by Combiflash (51%).
1
H NMR (400MHz, acetone-d6): δ
8.04 (d, 2H, J = 8 Hz), 7.34 (t, 8H, J = 8 Hz), 7.14 (m, 12H), 6.86 (d, 2H, J = 4 Hz), 6.45 (dd, 2H,
J = 8 Hz), 3.26 (s, 6H).
13
C NMR (100MHz, CDCl3): δ 162.1, 153.5, 151.8, 146.3, 146.0, 133.9,
132.5, 129.7, 126.4, 125.7, 125.3, 119.2, 111.6, 106.8. 28.7. m/z calculated for C43H32N4O3:
652.3 found by FAB: 653.5.
Synthesis
of
5-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-1,3-diethyl-2-
thioxodihydropyrimidine-4,6(1H,5H)-dione (DAA-Fl-6S). DAA-Fl (50 mg, 0.1 mmol) and 1,3diethyl-2-thiobarbituric acid (160 mg, 0.8 mmol) were dissolved in 2 mL acetic acid and 2 mL
acetic anhydride and refluxed overnight. The acetic acid and acetic anhydride were removed
under vacuum and the crude mixture was dissolved in DCM and washed twice with water and
1
once with saturated sodium bicarbonate. The product was purified by Combiflash (86%). HNMR (500 MHz, acetone-d6): δ 8.02 (d, J = 8.9 Hz, 2H), 7.38 (t, J = 7.8 Hz, 8H), 7.22-7.19 (m,
11H), 6.85 (d, J = 2.1 Hz, 2H), 6.45 (dd, J = 8.9, 2.2 Hz, 2H), 4.54-4.48 (m, 4H), 1.24 (t, J = 6.8
Hz, 6H).
13
C-NMR (126 MHz, acetone-d6): δ 160.4, 154.6, 146.7, 146.6, 135.0, 132.7, 130.6,
127.4, 126.5, 118.8, 111.8, 44.0, 43.5, 13.0, 12.3. m/z calculated for C45H36N4O2S: 696.3 found
by FAB: 697.6.
Synthesis
of
2-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-1H-indene-1,3(2H)-dione
(DAA-Fl-In). DAA-Fl (25 mg, 0.05 mmol) and 1,3-indandione (2 mg, 0.15 mmol) were dissolved
in 2 mL acetic acid and 2 mL acetic anhydride and refluxed overnight. The acetic acid and acetic
anhydride were removed under vacuum and the crude mixture was dissolved in DCM and
washed twice with water and once with saturated sodium bicarbonate. The product was purified
2 by Combiflash (45%).
1
H NMR (400MHz, acetone-d6): δ 8.60 (d, 2H, J = 8 Hz), 7.88 (m, 4H),
7.37 (t, 8H, J = 8 Hz), 7.17 (m, 12H), 6.99 (d, 2H, J = 4 Hz), 6.64 (dd, 2H, J = 8 Hz).
13
C NMR
(100MHz, CDCl3): δ 190.7, 152.5, 146.5, 145.6, 141.6, 134.3, 133.6, 131.2, 129.7, 126.4, 126.1,
124.8, 122.5, 120.1, 112.5. m/z calculated for C46H30N2O2: 642.2 found by FAB: 643.5.
Synthesis of 4-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-3-phenylisoxazol-5(4H)-one
(DAA-Fl-PI). DAA-Fl (110 mg, 0.2 mmol) and 3-phenyl-5-isoxazolone (192 mg, 1.2 mmol) were
dissolved in 2 mL acetic acid and 2 mL acetic anhydride and refluxed overnight. The acetic acid
and acetic anhydride were removed under vacuum and the crude mixture was dissolved in DCM
and washed twice with water and once with saturated sodium bicarbonate. The product was
1
purified by Combiflash (18%). H NMR (400MHz, acetone-d6): δ 8.72 (d, 1H, J = 8 Hz), 7.52 (dd,
2H, J = 8 Hz), 7.46-7.31 (m, 11H), 7.22-7.14 (m, 8H), 7.07 (dd, 4H, J = 8 Hz), 7.01 (d, 1H, J = 4
Hz), 6.91 (d, 1H, J = 4 Hz), 6.65 (dd, 1H, J = 8 Hz), 6.35 (d, 1H, J = 8 Hz), 5.98 (dd, 1H, J = 8
Hz).
13
C NMR (100MHz, acetone-d6): δ 171.4, 163.8 159.6, 154.4, 153.5, 146.9, 146.7, 146.0,
145.9, 133.7, 133.0, 132.3, 130.9, 130.7, 130.7, 130.6, 129.7, 129.3, 127.3, 127.1, 126.3, 126.3,
119.4, 118.2, 112.7, 112.4, 107.3. m/z calculated for C46H31N3O2: 657.2 found by FAB: 658.4.
3 3,6-bis(diphenylamino)-9H-fluoren-9-one (DAA-Fl)
O
N
ppm08
78
67
56
N
45
34
23
12
01
4 2-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)malononitrile (DAA-Fl-CN) NC
N
CN
N
ppm18
ppm0
78
150
67
56
100150
45
34
50100
23
12
050
5 5-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)trione (DAA-Fl-6O).
O
N
O
N
ppm2
8
ppm0 200
68
150200
N
O
N
46
100150
24
50100
050
6 5-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-1,3-diethyl-2-thioxodihydropyrimidine4,6(1H,5H)-dione (DAA-Fl-6S).
S
N
O
N
O
N
ppm28
ppm0 200
68
150200
N
46
100150
24
50100
050
7 Synthesis of 2-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-1H-indene-1,3(2H)-dione
(DAA-Fl-In)
O
O
N
ppm0
ppm0 200
8
N
68
150200
46
100150
24
50100
02
050
8 4-(3,6-bis(diphenylamino)-9H-fluoren-9-ylidene)-3-phenylisoxazol-5(4H)-one (DAA-Fl-PI)
N O
O
N
ppm0
ppm0 200
810
N
68
150200
46
100150
24
50100
02
050
9 References
[1]
B. Kobin, L. Grubert, S. Blumstengel, F. Henneberger, S. Hecht, J. Mater. Chem. 2012,
22, 4383-4390.
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