Facile synthesis of spirocyclic aromatic hydrocarbon derivatives based on o-halobiaryl route and domino reaction for deep-blue organic semiconductors

Article abstract of DOI:10.1021/ol900978x

Conventional o-halobiaryl and one-pot tandem protocols have been developed to synthesize naphthalene- and pyrene-containing spirofluorenes. Two pyrene substituents were installed using a Suzuki cross-coupling reaction to produce a series of spirofluorene-

Full text of DOI:10.1021/ol900978x

Supporting Information-Organic Letters
Facile Synthesis of Spirocyclic Aromatic Hydrocarbon Derivatives based on o-Halobiaryl Route
and Domino Reaction for Deep-blue Organic Semiconductors
Feng Liu, † Ling-Hai Xie, † Chao Tang, † Jing Liang, † Qing-Quan Chen, ‡ Bo Peng, † Wei Wei, *, † Yong Cao, ‡ and
Wei Huang *, †
Jiangsu Key Lab for Organic Electronics & Information Displays and Institute of Advanced Materials (IAM), Nanjing
University of Posts & Telecommunications (NUPT), 9 Wenyuan Road, Nanjing 210046, China, and Institute of
Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640, China
* To whom all correspondence should be addressed. Phone: +86 25 8586 6008. Fax: +86 25 8586 6999. E-mail address:
wei-huang@njupt.edu.cn/ iamww@fudan.edu.cn.
Experimental Section
Chemicals: n-BuLi, 2-bromopyrene, tetrakistriphenylphosphine palladium(0) were obtained from
Aldrich Chemical Co. and were used without further purification. THF and diethyl ether were dried
over sodium benzophenone ketyl anion radical and distilled under a dry nitrogen atmosphere
immediately prior to use. 2,7-dibromo-9,9'-spirobi[fluorene] (DBrSBF) ， 2,7-dibromospiro
[fluorene-9,9'-xanthene]
(DBrSFX),
2-bromopyrene,
4,4,5,5-tetramethyl-2-(pyren-1-yl)-
1,3,2-dioxaborolane, and 2,7-di(pyrenyl)spirobifluorene (DPSBF) were prepared as previously
reported.1
Characterization: 1H- and 13C-NMR in CDCl3 were recorded at 400 MHz using a Varian Mercury 400
plus spectrometer. Mass spectra was recorded with a Shimadzu GCMS-QP2010 plus spectrometer or a
Shimadzu AXIMA-CFR plus spectrometer. Elemental analyses were carried out in an elementar
Analysensysteme GmbH - vario EL III Element Analyzer. Absorption spectra (1 μM in CHCl3) were
measured with a Shimadzu UV-3150 spectrometer at 25°C, and emission spectra (1 μM in CHCl3)
were recorded with a Shimadzu RF-530XPC luminescence spectrometer upon excitation at the
absorption maxima in the argon-degassed CH2Cl2 solvent. Differential scanning calorimetry (DSC)
analyses were performed in a Shimadzu DSC-60A instrument, in which the sample was heated (10
°C/min) to 360 °C and then quenched with liquid nitrogen followed by heating (10°C/min) the
quenched sample during spectra collection. Thermogravimetric analyses (TGA) were conducted by a
Shimadzu DTG-60H under a heating rate of 10°C/min and a nitrogen flow rate of 20 cm3/min. Cyclic
1. (a) Xie L. H.; Fu T.; Hou X. Y.; Tang C.; Hua Y. R.; Wang R. J.; Si S. M.;Fan Q. L.; Lian-Hui Wang, Wei Wei, Bo Peng,
and Huang W. Tetrahedron Letters 2006, 47 (36), 6421. (b) Thompson, A. L. H.; Attar, A. A.; Diasb, F. B.; Monkman,
A. P. J. Mater. Chem. 2006, 16, 1046-1052. (c) Tsuboyama, A.; Iwawaki, H.; Furugori, M.; Mukaide, T.; Kamatani, J.;
Igawa, S.; Moriyama, T.; Miura, S.; Takiguchi, T.; Okada, S.; Hoshino, M.; Ueno, K. J. Am. Chem. Soc. 2003, 125,
12971-12979.
S1

voltammetric (CV) studies were made using an Eco Chemie BV. Electrochemical instruments. A
platinum-sheet working electrode, a platinum-wire counter electrode, and a silver/silver nitride
(Ag/AgNO3) reference electrode were used to form a three-electrode configuration. All electrochemical
experiments were carried out with a scan rate of 0.1 V/s under the nitrogen atmosphere at room
temperature in the CH2Cl2 solvent with 0.1 M tetrabutylammonium hexafluorophosphate (n-Bu4NPF6)
as the supporting electrolyte.
Quantum chemistry calculation: The quantum chemical calculations were performed using Gaussian
03, B.04 program. The ground state geometries were optimized by DFT/B3LYP method at 6-31G level.
The frontier orbital information is obtained. Zindo/S method was used to estimate the transition
energies (ΔEt) and oscillator strength (I), in the calculation, the lowest 12 transition states and their
oscillator strength were considered. Charge migration in organic solid is regarded as the hopping
process. The rate of the charge hopping rate kET can be estimated by Marcus formalism:
4π 2
h
1
kET =
t2
e−λ /4RT
4πλRT
where λ is internal reorganization energy which corresponding to the sum of geometry relaxation
energies upon going from the neutral-state geometry to the charged-state geometry and vice versa. t
represents the strength of intermolecular electronic coupling (transfer integrals) between adjacent
molecules, dictated largely by orbital overlap. Reorganization energies of the molecules are evaluated
by DFT/B3LYP method using 6-31G base set and the calculated values for hole transport and electron
transport are summarized in manuscript Table 2. The transfer integrals are evaluated as half the
splitting of the HOMO [LUMO] level for holes [electrons] in a dimmer formed by two molecules in
their ground state geometry. The dimmer model was built by stacking the pyrene groups face to face,
and d is the intermolecular distance (Figure S6). The results are shown in Figure S7. The electronic
splittings decrease exponentially when the intermolecular distance is increased. Short distances are thus
desirable to promote high hopping rates. And generally transfer integral for hole is larger than transfer
integral for electron.
Fabrication and characterization of Device: LED was fabricated on pre-patterned indium-tin oxide
(ITO) with sheet resistance 10-20 Ω/□. The substrate was ultrasonic cleaned with acetone, detergent,
deionized water, and 2-propanol. Oxygen plasma treatment was made for 5 min as the final step just
before
film
coating.
Onto
the
ITO
glass
was
spin-coated
a
layer
of
polyethylenedioxythiophene-polystyrene sulfonic acid (PEDOT: PSS) film with thickness of 40 nm
from its aqueous dispersion. PEDOT: PSS film was dried at 80 °C for 12 h in the vacuum oven. The
solution of the polymer was prepared under nitrogen atmosphere and spin-coated on to PEDOT: PSS
S2

layer. Typical thickness of the emitting layer was 80 nm and heated at 60 °C for 30 min. Then a thin
layer of 2 nm CsF as the electron injection cathode and the subsequent 120 nm thick aluminum
protection layers were thermally deposited by vacuum evaporation through a mask at a base pressure
below 4 × 10-4 Pa. The cathode area defines the active area of the device. The typical active area of the
devices in this study is 0.17 cm2. The EL layer spin coating process and the device performance tests
were carried out within a glove box under nitrogen atmosphere. Current-voltage (I-V) characteristics
were recorded with a Keithley 236 source meter. EL spectra were measured by a PR 705 photometer
(Photo Research). The external quantum efficiencies were determined by a Si photodiode with
calibration in an integrating sphere (IS080, Labsphere).
Preparation of 1-(2-bromophenyl)naphthalene (2): 1-bromonaphthalene (4.14 g, 20 mmol) was
o
dissolved in distillated THF (50 mL) in capped bottle. The temperature was kept in -78 C using dry
ice/acetone bath. BuLi (12.5 mL，20 mmol) was added to the bottle and stirred for 1.5 h under -78
oC. Then trimethyl borate (4.2 g, 50 mmol) was added quickly, stirr under -78 oC for 1.5 h and then run
overnight under room temperature. HCl (2M, 200 ml) was added and stirred for 5 h. The solution was
extracted with dichloromethane, washed with water, dried with anhydrous MgSO4. The solvent was
removed by rotary evaporation, white solid was obtained. 1,2-dibromobenzene ( 4.67g, 20 mmol) was
added to the crude product, Pd(PPh3)4 (40mg), K2CO3 (2M, 10 ml) and degassed toluene (40 ml) were
o
added. Run the reaction under 85 C for 24 h under N2 without light exposure. The reaction solution
was extracted with dichloromethane, washed with water, dried with anhydrous MgSO4. The solvent
was removed by rotary evaporation, and the residue was purified by column chromatography using
CH2Cl2/petroleum ether (1 : 10) as eluent to obtain the white solid (3.34 g, 59%). 1HNMR (400 MHz,
CDCl3) δ(ppm): 7.93 (d, 2H); 7.75 (d, 1H); 7.55 (t, 1H); 7.51-7.40 (m, 4H); 7.38 (d, 2H); 7.32 (t, 1H).
MALDI-TOF-MS (m/z): Calcd. for C16H11Br 283.2, found 283.4.
Preparation of 1-(2-bromophenyl)pyrene (4): 1-bromopyrene (2.81 g, 10 mmol) was dissolved in
o
distillated THF (30 mL) in capped bottle. The temperature was kept in -78 C using dry ice/acetone
o
bath. BuLi (6.25 mL, 10 mmol) was added to the bottle and stirred for 1.5 h under -78 C. Then
trimethyl borate (2.1 g, 25 mmol) was added quickly, stirr under -78 oC for 1.5 h and then run overnight
under room temperature. HCl (2M, 100 ml) was added and stirred for 5 h. The solution was extracted
with dichloromethane, washed with water, dried with anhydrous MgSO4. The solvent was removed by
rotary evaporation, white solid was obtained. 1,2-dibromobenzene ( 2.33g, 10 mmol) was added to the
crude product, PdP(Ph3)4 (40mg), K2CO3 (2M, 10 ml) and degassed toluene (40 ml) were added. Run
the reaction under 85 oC for 24 h under N2 without light exposure. The reaction solution was extracted
with dichloromethane, washed with water, dried with anhydrous MgSO4. The solvent was removed by
S3

rotary evaporation, and the residue was purified by column chromatography using CH2Cl2/petroleum
1
ether (1 : 8) as eluent to obtain the white solid (2.28 g, 64%). H-NMR (400 MHz, CDCl3): δ (ppm)
8.29 (d, 1H), 8.25 (m 2H), 8.16 (d, 2H), 8.08 (m, 2H), 8.00 (d, 1H), 7.87 (m, 2H), 7.54 (m, 2H), 7.40(m,
1H). MALDI-TOF-MS (m/z): Calcd. for C22H13Br 357.2, found 357.1.
Preparation
of
2',7'-dibromospiro[benzo[c]fluorene-7,9'-fluorene]
(DBrSBFF):
1-(2-bromophenyl)naphthalene (2) (2.83g, 10 mmol) was dissolved in dry THF (25 mL) in capped
o
bottle. The temperature was kept in -78 C using dry ice/acetone bath. BuLi (6.25 mL，10 mmol)
was added to the bottle and stirred for 1.5 h under -78 oC. Then, the reaction solution was taken out by
syringe and was added to 2,7-dibromofluorenone (3.37g, 10 mmol) THF solution. The reaction mixture
was extracted with dichloromethane, washed with water, dried with anhydrous MgSO4. The solvent
was removed by rotary evaporation, white solid was obtained. The crude product was dissolved in
o
AcOH, several drops of concentrated HCl was added. Keep the reaction under 110 C for 24 h. The
reaction solution was extracted with dichloromethane, washed with water, dried with anhydrous
MgSO4. The solvent was removed by rotary evaporation, and the residue was purified by column
chromatography using CH2Cl2/petroleum ether (1 : 6) as eluent to obtain the white solid (3.88 g, 74%).
1H-NMR (500 MHz, CDCl3): δ (ppm) 8.85 (d, 1H), 8.45 (d 1H), 7.93 (d, 1H), 7.73-7.65 (m, 4H), 7.56
(t, 1H), 7.51 (d, 3H), 7.19 (t, 1H), 6.82-6.78(m, 4H). MALDI-TOF-MS (m/z): Calcd. for C29H16Br2
524.3, found 524.9.
Preparation
of
2,7-dibromospiro[fluorene-9,7-indeno[1,2-a]pyrene]
(DBrSIPF):
1-(2-bromophenyl)pyrene (4) (2.28g, 6 mmol) was dissolved in distillated THF (25 mL) in capped
bottle. The temperature was kept in -78 oC using dry ice/acetone bath. n-BuLi (3.75 mL，6 mmol) was
o
added to the bottle and stirred for 1.5 h under -78 C. Then, the reaction solution was taken out by
syringe and was added to 2,7-dibromofluorenone (2.02g, 6 mmol) THF solution. The reaction mixture
was extracted with dichloromethane, washed with water, dried with anhydrous MgSO4. The solvent
was removed by rotary evaporation, white solid was obtained. The crude product was dissolved in
o
AcOH, several drops of concentrated HCl was added. Keep the reaction under 110 C for 24 h. The
reaction solution was extracted with dichloromethane, washed with water, dried with anhydrous
MgSO4. The solvent was removed by rotary evaporation, and the residue was purified by column
chromatography using CH2Cl2/petroleum ether (1 : 6) as eluent to obtain the white solid (2.48 g, 69%).
1H-NMR (400 MHz, CDCl3): δ (ppm) 9.12 (d, 1H), 8.66 (d 1H), 8.37 (d, 2H), 8.26 (d, 1H), 8.18 (t, 1H),
8.10-7.99 (m, 3H), 7.83-7.74 (m, 4H), 7.59-7.51(m, 4H), 7.25 (d, 1H), 6.88 (s, 2H). MALDI-TOF-MS
(m/z): Calcd. for C35H20Br2 600.3, found 600.7.
Preparation of 2',7'-dibromospiro[dibenzo[c,h]xanthene-7,9-fluorene] (DBrSDBXF): A mixture of
2,7-dibromofluorenone (6.523 g, 19.3 mmol, 1 equiv), naphthalen-1-ol (11.116 g, 77.2 mmol, 4 equiv),
S4

and methane sulfonic acid (MeSO3H, 5.0 ml, 7.41 g, 77.2 mmol, 4 equiv ) was heated at 150 °C under
nitrogen for 24 h. the reaction mixture was then slowly add into water (50 ml) and extracted with
dichloromethane. The combined extracts were dried over MgSO4, evaporated, and recrystallized with
1
ethyl acetate to afford white solid (9.34 g, 82%). H-NMR (500 MHz, CDCl3): δ (ppm) 8.77 (d, 2H),
7.78 (d, 2H), 7.74-7.69 (m, 4H), 7.59 (t, 2H), 7.53 (d, 2H), 7.31 (d, 2H), 7.27 (s, 2H), 6.38 (d, 2H).
MALDI-TOF-MS (m/z): Calcd. for C33H18Br2O 590.3, found 590.7.
Preparation of 2,7-di(pyren-1-yl)spiro[fluorene-9,7-benzo[c]fluorene] (DPSBFF): In a 50 ml bottle,
4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane (1.0 g, 3.0 mmol), DBr-SNPF (0.786 g, 1.5
mmol), Pd(PPh3)4 (0.02 mmol), degassed toluene (50 mL) and K2CO3 (2 M, 10 ml) was added. The
bottle was capped and protected with N2. Light exposure was avoided. Run the reaction under 90 °C for
48 h. The reaction solution was extracted with dichloromethane. The solvent was removed by rotary
evaporation, and the residue was purified by column chromatography using CH2Cl2/petroleum ether (1 :
1
4) as eluent to obtain the white solid (0.771 g, 67%). H-NMR (500 MHz, CDCl3): δ (ppm) 8.77 (d,
1H), 8.38 (d, 1H), 8.17-8.07 (m, 10H), 8.02-7.90 (m, 10H), 7.85 (d, 2H), 7.76 (d, 3H), 7.62 (t, 1H),
7.51 (t, 1H), 7.46 (t, 1H), 7.15 (t, 2H), 7.05 (s, 2H). MALDI-TOF-MS (m/z): Calcd. for C61H34 766.9,
found 767.4. Anal. Calcd. C, 95.53; H, 4.47. found C, 95.45; H, 4.51.
Preparation of 2,7-di(pyren-1-yl)spiro[fluorene-9,7-indeno[1,2-a]pyrene] (DPSIPF): In a 50 ml
bottle, 4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane (1.0 g, 3.0 mmol), DBrSPPF (0.900 g,
1.5 mmol), Pd(PPh3)4 (0.02 mmol), degassed toluene (50 mL) and K2CO3 (2M, 10 ml) was added. The
bottle was capped and protected with N2. Light exposure was avoided. Run the reaction under 90 °C for
48 h. The reaction solution was extracted with dichloromethane. The solvent was removed by rotary
evaporation, and the residue was purified by column chromatography using CH2Cl2/petroleum ether (1 :
1
4) as eluent to obtain the greenish white solid (0.971 g, 77%). H-NMR (500 MHz, CDCl3): δ (ppm)
8.66 (d, 1H), 8.31 (d, 1H), 8.22-8.11 (m, 8H), 8.06-7.92 (m, 16H), 7.85 (d, 2H), 7.76 (d, 2H), 7.65 (s,
1H), 7.50 (s, 1H), 7.40 (t, 1H), 7.20 (t, 1H), 7.08-7.03 (m, 2H). MALDI-TOF-MS (m/z): Calcd. for
C67H36 841.0, found 841.4. Anal. Calcd. C, 95.69; H, 4.31. found C, 95.49; H, 4.48.
Preparation of 2,7-di(pyren-1-yl)spiro[fluorene-9,9-xanthene] (DPSFX): In a 50 ml bottle,
4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane (1.0 g, 3.0 mmol), DBr-SFX (0.735 g, 1.5
mmol), Pd(PPh3)4 (0.02 mmol), degassed toluene (50 mL) and K2CO3 (2M, 10 ml) was added. The
bottle was capped and protected with N2. Light exposure was avoided. Run the reaction under 90 °C for
48 h. The reaction solution was extracted with dichloromethane. The solvent was removed by rotary
evaporation, and the residue was purified by column chromatography using CH2Cl2/petroleum ether (1 :
1
4) as eluent to obtain the yellowish white solid (0.78 g, 72%). HNMR (400 MHz, CDCl3)δ(ppm):
8.19-8.13 (m, 6H); 8.09 – 8.07 (d, 8H); 8.02 - 7.91 (m, 6H); 7.75 - 7.73 (d, 2H); 7.54 (s, 2H); 7.24 -
S5

7.17 (m, 4H); 6.95 (t, 2H); 6.81 (d, 2H). MALDI-TOF-MS (m/z): Calcd. for C57H32O 732.9, found
733.2. Anal. Calcd. C, 93.42; H, 4.40; O, 2.18. found C, 93.25; H, 4.62.
Preparation of 2,7- di(pyren-1-yl)spiro[fluorene-9,7-dibenzo[c,h]xanthene] (DPSDBXF): In a 50
ml bottle, 4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane (1.0 g, 3.0 mmol), DBr-SNF (0.885 g,
1.5 mmol), Pd(PPh3)4 (0.02 mmol), degassed toluene (50 mL) and K2CO3 (2M, 10 ml) was added. The
bottle was capped and protected with N2. Light exposure was avoided. Run the reaction under 90 °C for
48 h. The reaction solution was extracted with dichloromethane. The solvent was removed by rotary
evaporation, and the residue was purified by column chromatography using CH2Cl2/petroleum ether (1 :
4) as eluent to obtain the white solid (0.962 g, 77%). 1HNMR (400 MHz, CDCl3)δ(ppm): 8.70 (d, 2H);
8.15 (t, 4H); 8.07 (m, 6H); 8.01 (s, 4H); 7.95 (t, 2H); 7.88 - 7.76 (m, 8H); 7.63 (t, 2H); 7.53 (d, 4H);
7.46 (d, 2H); 6.82 (d, 2H). MALDI-TOF-MS (m/z): Calcd. for C65H36O 833.0, found 833.4. Anal.
Calcd. C, 93.72; H, 4.36; O, 1.92. found C, 93.65; H, 4.42.
S6

Table S1. ZINDO/SCI calculated lowest transition energies (ΔEt /eV) and oscillator strengths (I /a.u.)
Excited
DPSBF
DPSBFF
DPSIPF
State
ΔEt
I
ΔEt
I
ΔEt
I
1
2
3
4
5
6
7
8
3.1816
3.2939
3.3106
3.3330
3.7583
4.0135
4.0171
4.0301
4.0537
4.1019
4.2242
4.3316
1.9035
0.0691
0.0514
0.0512
0.3699
0.2433
0.0129
0.0010
0.0009
0.0201
0.0034
0.0126
3.1732
3.2906
3.3096
3.3293
3.5196
3.7289
3.7427
4.0093
4.0262
4.0497
4.0934
4.1636
1.8955
0.0934
0.0505
0.0605
0.3168
0.0317
0.3485
0.0224
0.0027
0.0022
0.0261
0.0002
3.1157
3.1764
3.2285
3.2952
3.3099
3.3343
3.7499
3.9683
4.0119
4.0276
4.0436
4.0512
0.7025
1.9802
0.1237
0.0522
0.0485
0.0524
0.3497
0.2159
0.0195
0.0016
0.0023
0.0027
9
10
11
12
Table S2. ZINDO/SCI calculated lowest transition energies (ΔEt /eV) and oscillator strengths (I /a.u.)
Excited
State
DPSFX
DPSDBXF
ΔEt
ΔEt
I
I
1
2
3
4
5
6
7
8
3.1791
3.2943
3.3108
3.3322
3.7465
4.0034
4.0290
4.0490
4.0953
4.3121
4.3227
4.3469
1.9152
0.0699
0.0479
0.0506
0.3532
0.0172
0.0011
0.0001
0.0156
0.0315
0.0159
0.1150
3.1787
3.2921
3.3105
3.3288
3.7368
3.7469
3.7549
3.7812
3.9864
4.0301
4.0439
4.0579
1.9093
0.1006
0.0480
0.0641
0.0906
0.0004
0.3686
0.0995
0.0758
0.0008
0.0166
0.0469
9
10
11
12
Figure S-1. Pyrene stacked dimmer model of DPSFX
S7

0.3
0.2
0.1
0.4
0.2
DPSBF
0.0
0.4
0.0
0.3
0.2
0.1
0.2
DPSBFF
DPSIPF
0.0
0.4
0.0
0.3
0.2
0.1
0.2
0.0
0.4
0.0
0.3
0.2
0.1
0.2
DPSFX
0.0
0.4
0.0
0.3
0.2
0.1
0.0
0.2
0.0
DPSDBXF
3.5
4.0
4.5
5.0
5.5
6.0
6.5 3.5
4.0
4.5
5.0
5.5
6.0
6.5
Distance (angs.)
Distance (angs.)
Figure S-2. Transfer integrals of the molecules
S8

Figure S-3. HOMO-LUMO of materials
S9

Br
Br
DBrSBFF
9.00
ppm (t1)
8.50
8.00
7.50
7.00
6.50
Figure S-4. 1H NMR of DBrSBFF
Br
Br
DBrSIPF
9.00
8.50
8.00
7.50
7.00
ppm (t1)
Figure S-5. 1H NMR of DBrSIPF
S10

O
Br
Br
DBrSDBXF
9.00
ppm (t1)
8.50
8.00
7.50
7.00
6.50
Figure S-6. 1H NMR of DBrSDBXF
DPSBF
8.00
7.50
7.00
ppm (t1)
Figure S-7. 1H NMR of DPSBF
S11

DP-SNPF-766.9
Data: DP-SNPF-766.9-TOF0001.D2 25 Aug 2006 16:12 Cal: tof 14 Oct 2005 11:47
Kratos PC Axima CFRplus V2.4.0: Mode reflectron, Power: 82, P.Ext. @ 766 (bin 68)
%Int.
3.7 mV[sum= 127 mV] Profiles 1-34 Smooth Av 20 -Baseline 80
767.3
100
90
80
70
60
50
40
30
20
DPSBFF
10
0
200
400
600
800
1000
1200
1400
Mass/Charge
Figure S-8. MALDI-TOF-MS of DPSBFF
DPSBFF
8.50
8.00
7.50
7.00
m(t1)
Figure S-9. 1H NMR of DPSBFF
S12

FL-478
Data: FL-8400001.O8 8 Jun 2006 11:34 Cal: 060222-zheng 22 Feb 2006 10:57
Kratos PC Axima CFRplus V2.4.0: Mode reflectron, Power: 80, P.Ext. @ 840 (bin 71)
%Int.
112 mV[sum= 5829 mV] Profiles 1-52 Smooth Av 20 -Baseline 80
841.0
100
90
80
70
60
50
40
30
20
DPSIPF
10
0
200
400
600
800
1000
1200
1400
Mass/Charge
Figure S-10. MALDI-TOF-MS of DPSIPF
DPSIPF
8.50
8.00
7.50
7.00
pm (t1)
Figure S-11. 1H NMR of DPSIPF
S13

DP-SFX-732.8
Data: DP-SFX-732.8-TOF0001.E2 25 Aug 2006 16:14 Cal: tof 14 Oct 2005 11:47
Kratos PC Axima CFRplus V2.4.0: Mode reflectron, Power: 82, P.Ext. @ 732 (bin 66)
%Int.
4.4 mV[sum= 83 mV] Profiles 1-19 Smooth Av 20 -Baseline 80
733.2
100
90
O
80
70
60
50
40
30
20
DPSFX
10
0
200
400
600
800
1000
1200
1400
Mass/Charge
Figure S-12. MALDI-TOF-MS of DPSFX
O
DPSFX
8.00
7.50
7.00
6.50
pm (t1)
Figure S-13. 1H NMR of DPSFX
S14

DP-SNF-832.98
Data: DP-SNF-832.980001.F2 25 Aug 2006 16:17 Cal: tof 14 Oct 2005 11:47
Kratos PC Axima CFRplus V2.4.0: Mode reflectron, Power: 88, P.Ext. @ 832 (bin 70)
%Int.
31 mV[sum= 1568 mV] Profiles 1-51 Smooth Av 20 -Baseline 80
833.4
100
90
O
80
70
60
50
40
30
20
DPSDBXF
10
0
200
400
600
800
1000
1200
1400
Mass/Charge
Figure S-14. MALDI-TOF-MS of DPSFDBX
O
DPSDBXF
8.50
8.00
7.50
7.00
ppm (t1)
Figure S-15. 1H NMR of DPSDBXF
S15