High ionization potential conjugated polymers

Article abstract of DOI:10.1021/ja052828x

We report the synthesis of a series of poly(p-phenylene ethynylene)s (PPEs) with high ionization potentials and associated high excited-state electron affinities. Their photophysical properties were investigated using steady-state and time-resolved fluorescence techniques. The ionization potentials of the polymer thin films were determined using ultraviolet photoelectron spectroscopy (UPS), and those with the highest ionization potentials displayed high sensitivity for the detection of electron-donating aromatic compounds. The effects of sterics, chemical structure, and electronic properties on the polymers' sensory responses were investigated by fluorescence quenching experiments in both solution and solid thin films. In addition, we report that in some cases the excited-state charge-transfer complexes (exciplexes) of the PPEs with analytes were observed. These latter effects provide promising opportunities for the formation of sensitive and selective chemical sensors.

Full text of DOI:10.1021/ja052828x

Published on Web 08/06/2005
High Ionization Potential Conjugated Polymers
Youngmi Kim,‡ James E. Whitten,*,† and Timothy M. Swager*,‡
Contribution from the Department of Chemistry and Institute for Soldier Nanotechnologies,
Massachusetts Institute of Technology, 77 Massachusetts AVenue,
Cambridge, Massachusetts 02139, and Department of Chemistry and Center for AdVanced
Materials, UniVersity of Massachusetts Lowell, One UniVersity AVenue,
Lowell, Massachusetts 01854
Received April 30, 2005; E-mail: James_Whitten@uml.edu; tswager@mit.edu
Abstract: We report the synthesis of a series of poly(p-phenylene ethynylene)s (PPEs) with high ionization
potentials and associated high excited-state electron affinities. Their photophysical properties were
investigated using steady-state and time-resolved fluorescence techniques. The ionization potentials of
the polymer thin films were determined using ultraviolet photoelectron spectroscopy (UPS), and those with
the highest ionization potentials displayed high sensitivity for the detection of electron-donating aromatic
compounds. The effects of sterics, chemical structure, and electronic properties on the polymers’ sensory
responses were investigated by fluorescence quenching experiments in both solution and solid thin films.
In addition, we report that in some cases the excited-state charge-transfer complexes (exciplexes) of the
PPEs with analytes were observed. These latter effects provide promising opportunities for the formation
of sensitive and selective chemical sensors.
Introduction
developing high excited-state electron affinity CPs due to their
potential to expand the range of chemosensory responses, an
Fluorescent conjugated polymers (CPs) have emerged as an
important class of sensory materials for chemical and biochemi-
cal targets.1 This interest has been driven by the ability of CPs
to create large signal amplification relative to small molecule
chemosensors due to the delocalization and rapid diffusion of
excitons throughout the individual CP chains in solution2 and
in thin films.3 Building upon these principles, there is an ever-
increasing demand for CPs with higher sensitivity and the ability
to selectively target a wider scope of analytes. Receptor-coupled
transduction schemes have been devised to impart selectivity
to CP chemosensors;4 however, much less work has been
devoted to gaining selectivity by changing the excited-state
electron affinity of the polymers. The vast majority of lumi-
nescent CPs investigated so far has been of the low ionization
potential variety (i.e., p-type materials), and the most efficient
sensory transduction schemes involve electron transfer from the
excited CP to an electron acceptor.5 We have been engaged in
increasing interest in n-type materials for field effect transistors,6
their utility as the electron-transporting elements in polymer light
emitting devices,7 and due to their potential to enhance
photovoltaic devices.8
Previously, our group developed ultrasensitive sensory ma-
terials based on pentiptycene-containing poly(p-phenylene ethy-
nylene)s, which exploited fluorescence quenching upon response
to vapors of electron-accepting analytes, such as 2,4,6-trinitro-
toluene (TNT) and 2,4-dinitrotoluene (DNT).3 The detection
mechanism is fluorescence quenching through nonbonding
electrostatic associations between the electron-rich polymer and
the electron-poor nitroaromatic quenchers. On the basis of this
success, we have similarly been interested in whether a
reciprocal process can be developed that is sensitive to electron-
rich aromatics of biological importance, such as indoles and
phenols.9 We report herein PPEs designed with [2.2.2] bicyclic
ring systems incorporating electron-withdrawing perfluoroalkyl
groups (Chart 1). Similar to our earlier designs,5 the noncom-
pliant [2.2.2] bicyclic ring system is effective in preventing π-π
‡ Massachusetts Institute of Technology.
† University of Massachusetts Lowell.
(1) (a) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. ReV. 2000, 100,
2537-2574. (b) Huang, H.; Wang, K.; Tan, W.; An, D.; Yang, X.; Huang,
S.; Zhai, Q.; Zhou, L.; Jin, Y. Angew. Chem., Int. Ed. 2004, 43, 5635-
5638.
(6) (a) Facchetti, A.; Yoon, M.-H.; Stern, C. L.; Hutchison, G. R.; Ratner, M.
A.; Marks, T. J. J. Am. Chem. Soc. 2004, 126, 13480-13501. (b) Babel,
A.; Jenekhe, S. A. J. Am. Chem. Soc. 2003, 125, 13656-13657.
(7) (a) Yu, L.-S.; Chen, S.-A. AdV. Mater. 2004, 16, 744-748. (b) Hughes,
G.; Bryce, M. R. J. Mater. Chem. 2005, 15, 94-107. (c) Kulkarni, A. P.;
Tonzola, C. J.; Babel, A.; Jenekhe, S. A. Chem. Mater. 2004, 16, 4556-
4573.
(8) (a) Alam, M. M.; Jenekhe, S. A. Chem. Mater. 2004, 16, 4647-4656. (b)
Neuteboom, E. E.; Meskers, S. C. J.; van Hal, P. A.; van Duren, J. K. J.;
Meijer, E. W.; Janssen, R. A. J.; Dupin, H.; Pourtois, G.; Cornil, J.;
Lazzaroni, R.; Bre´das, J.-L.; Beljonne, D. J. Am. Chem. Soc. 2003, 125,
8625-8638.
(9) (a) Bernardo, A. R.; Stoddart, J. F.; Kaifer, A. E. J. Am. Chem. Soc. 1992,
114, 10624-10631. (b) Deranleau, D. A.; Schwyzer, R. Biochemistry 1970,
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(2) Zhou, Q.; Swager, T. M. J. Am. Chem. Soc. 1995, 117, 7017-7018.
(3) Yang, J.-S.; Swager, T. M. J. Am. Chem. Soc. 1998, 120, 5321-5322.
(4) For recent examples not covered in earlier reviews, see: (a) Kim, J.;
McQuade, D. T.; McHugh, S.; Swager, T. M. Angew. Chem., Int. Ed. 2000,
39, 3868-3872. (b) Vigalok, A.; Zhu, Z.; Swager, T. M. J. Am. Chem.
Soc. 2001, 123, 7917-7918. (c) Takeuchi, M.; Shioya, T.; Swager, T. M.
Angew. Chem., Int. Ed. 2001, 40, 3372-3376. (d) Vigalok, A.; Swager, T.
M. AdV. Mater. 2002, 14, 368-371. (e) Yu, H.-H.; Pullen, A. E.; Bu¨schel,
M. G.; Swager, T. M. Angew. Chem., Int. Ed. 2004, 43, 3700-3703.
(5) (a) Yang, J.-S.; Swager, T. M. J. Am. Chem. Soc. 1998, 120, 11864-11873.
(b) Chen, L.; McBranch, D. W.; Wang, H.-L.; Helgeson, R.; Wudl, F.;
Whitten, D. G. D. Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 12287-12292.
9
12122
J. AM. CHEM. SOC. 2005, 127, 12122-12130
10.1021/ja052828x CCC: $30.25 © 2005 American Chemical Society

High Ionization Potential Conjugated Polymers
A R T I C L E S
Chart 1
benzene. Monomer 6 is obtained in 79% overall yield by copper-
promoted coupling reactions between perfluoroalkyl iodides and
aromatic halides in DMSO followed by bromination (Scheme
3). The polymers shown in Chart 1 were synthesized by Pd-
(0)-catalyzed coupling reactions of diacetylene derivatives and
diiodo or dibromo monomers having perfluoroalkyl or alkoxy
substituents. Most of the polymers were completely soluble in
common organic solvents, such as THF, chloroform, dichlo-
romethane, and chlorobenzene. However, P-2 and P-9, with
(bis)trifluoromethyl groups on the phenyl ring, had limited
solubility, which could be dramatically improved by the addition
of bulky tert-butyl groups on the pentiptycene moiety as P-4.12
The photophysical properties and molecular weights of the
resulting polymers are summarized in Table 1. The relative
number average molecular weights (Mn) were estimated by gel
permeation chromatography (GPC) relative to polystyrene
standards (THF solvent) and ranged from 17 000 to 28 000
g/mol with polydispersity indices (Mw/Mn) from 1.2 to 2.9.
Photophysical Properties. The photophysical characteristics
of the polymers were studied both in chloroform solution and
in the solid state. The absorption maxima (λmax,abs), the emission
maxima (λmax,em), the extinction coefficients at the maximum
wavelengths (ꢀmax), fluorescence quantum yields (ΦF) in solu-
tion, and optical HOMO-LUMO energy gaps (Eg) are given
in Table 1. The latter were measured as the threshold of the
long wavelength side of the absorption peaks. The solution
absorption spectra of all polymers lack fine structure, whereas
the fluorescence spectra display clear vibronic peaks at room
temperature. The emission maxima of the thin films generally
display a slight red shift relative to those obtained in chloroform
solution. However, the absorption spectra of polymers containing
perfluoroalkyl groups (P-3, P-4, P-5, P-8, and P-10) display
nearly identical maxima in solution and the solid state. The
greater sensitivity of the emission maxima is likely the result
of enhanced energy migration in thin films, which results in
site-selective fluorescence from minority polymer segments with
lower band gaps and greater conjugation lengths.13 The π-π*
transitions of all of the materials are strongly allowed and give
rise to large molar (per repeating unit) absorption coefficients
(ꢀ, Table 1).
stacking between the conjugated polymer chains and introduces
porosity of molecular dimensions that allows for rapid diffusion
of analytes into and out of polymer thin films. The perfluoro-
alkyl groups are highly stable and powerful electron-withdraw-
ing substituents,10 and we have produced new versatile electron-
deficient CPs that are effective chemosensors for electron-rich
aromatic compounds. The ionization potentials of the polymer
films were determined using ultraviolet photoelectron spectros-
copy (UPS), and these properties are related to their photooxi-
dation behavior. The combined analysis provides an under-
standing for the design of highly emissive and high ionization
potential materials for sensory functions.
Results and Discussion
Synthesis. PPEs containing the [2.2.2] bicyclic ring systems
were targeted to increase polymer solubility and solid-state
quantum yields (Chart 1). Two types of structures were used:
pentiptycenes-based [2.2.2] bicyclic ring systems (P-1-P-5) and
related [2.2.2] systems wherein one of the phenyl rings in the
pentiptycene structures is replaced by an electron-poor alkene
(P-6-P-10). The latter groups serve to increase the polymer’s
ionization potential and excited-state electron affinity by a
combination of hyperconjugative and inductive interactions.11
The syntheses of pentiptycene monomers have been reported
elsewhere.5 Scheme 1 summarizes an analogous synthesis
leading to diacetylene monomers with electron-withdrawing
[2.2.2] bicyclic ring systems, and Schemes 2 and 3 present our
syntheses of the halide monomers. Monomer 3 is synthesized
in Scheme 1 with an overall yield of 76%. This sequence
involves a Diels-Alder reaction in xylene that assembles
nonstereospecifically the [2.2.2.] bicyclic ring system, and
deprotection with TBAF yields the key diethynyl monomer 3
for copolymerization with dihalide monomers by the Sonogash-
ira-Hagihara reaction. The exact isomeric structures of mono-
mers 3-a and 3-b were determined by single-crystal X-ray
structures (Figure 1). Monomer 4 is synthesized in one step by
iodination of commercially available 1,4-bis(trifluoromethyl)-
Figure 2 illustrates the absorption and emission spectra of
P-1 and P-3 in chloroform solutions and as thin films. The
spectra of P-1 and P-3 are, respectively, representative of the
polymers containing alkoxy-substituted phenyl rings and the
polymers containing perfluoroalkyl-substituted phenyl rings. P-1
displays an absorption maxima at 432 nm and emission maxima
at 453 nm with a low energy 0-1 peak at 482 nm, giving a
vibrational splitting of 1330 cm-1 consistent with CdC vibra-
tions.14 The extinction coefficients (based upon the molar
repeating units) are 28 000 M-1 cm-1 for P-1, 50 500 M-1 cm-1
for P-6, and 72 000 M-1 cm-1 for P-8. As revealed by the
absorption and emission spectra, the replacement of alkoxy
groups in P-1 with perfluoroalkyl groups in P-3 leads to a 40
nm blue shift in λmax,abs to 395 nm (ꢀ ) 50 000 M-1 cm-1).
The fluorescence spectrum of P-3 in chloroform displays its
maximum at 438 nm and a shoulder at 466 nm, indicative of
(12) Long, T. M.; Swager, T. M. J. Am. Chem. Soc. 2003, 125, 14113-14119.
(13) (a) Qiu, S.; Lu, P.; Liu, X.; Shen, F.; Liu, L.; Ma, Y.; Shen, J.
Macromolecules 2003, 36, 9823-9829. (b) Blatchford, J. W.; Jessen, S.
W.; Lin, L.-B.; Gustafson, T. L.; Fu, D.-K.; Wang, H.-L.; Swager, T. M.;
MacDiarmid, A. G.; Epstein, A. J. Phys. ReV. B 1996, 54, 9180-9189.
(14) Bush, T. E.; Scott, G. W. J. Phys. Chem. 1981, 85, 144-146.
(10) Krebs, F. C.; Spanggaard, H. J. Org. Chem. 2002, 67, 7185-7192.
(11) Kim, Y.; Zhu, Z.; Swager, T. M. J. Am. Chem. Soc. 2004, 126, 452-453.
9
J. AM. CHEM. SOC. VOL. 127, NO. 34, 2005 12123

A R T I C L E S
Kim et al.
Scheme 1. Synthetic Route to Monomers 3-a and 3-ba
a (a) (i) LiCCSi(isopropyl)3, 0-25 °C; (ii) SnCl2‚2H2O, 50% acetic acid, acetone, 25 °C, 24 h, 92%. (b) Dimethylacetylenedicaboxylate or hexafluorobutyne,
xylene, 140 °C, 48 h, 90%. (c) TBAF, THF, 25 °C, 0.5 h, 92%.
Scheme 2. Synthetic Route to Monomer 4a
substituted PPEs. This similarity does not parallel the larger
energy increase in the absorption maximum and is a reflection
of the conformational disorder of the perfluoroalkyl systems.
Interestingly, the large steric bulk of tert-butyl groups on the
pentiptycene moiety (P-3 vs P-4 and P-5) does not appear to
cause an increase or decrease in the band gap. This result
confirms that substitutions on the pendant phenyl rings do not
a (a) Periodic acid, KI/H2SO4, 75 °C, 5 h, 65%.
disturb the conformation of the polymer chain. Notably, all
Scheme 3. Synthetic Route to Monomer 6a
polymers displayed high fluorescence quantum yields, and it
appears that the conformational disorder and relaxations as-
sociated with the perfluoroalkyl groups do not promote nonra-
diative processes.
All of the polymers except P-7 displayed similar shapes for
emission curves in both solution and solid state, thereby
indicating the absence of strong interchain electronic couplings.
In the case of P-7, we observed an unusually strong red-shifted
broad peak in emission spectra in thin films, although its
emission in dilute solution was similar to that of the other
polymers. The description of this behavior is beyond the scope
of this present study, and an expanded investigation is underway
on a series of related materials.15
a (a) C8F17I, Cu, DMSO, 2,2′-bipyridine, 70 °C, 3 days, 90%. (b) H2SO4/
TFA (0.3 v/v), NBS, 60 °C, 2 days, 88%.
Ionization Potential Determination. Ultraviolet photoelec-
tron spectroscopy (UPS) using a He I (hν ) 21.22 eV) excitation
source and a concentric hemispherical electron energy analyzer
was used to measure the ionization potentials of thin (ca. 100-
300 Å) polymer films spin-coated on gold-covered silicon
substrates. The ionization potential, or work function of the
surface, was calculated by measuring the width of the UPS
spectrum and subtracting it from the photon energy.16
Figure 3A shows UPS spectra for the P-1, P-3, and P-10
films, which are typical of the spectra observed. Figure 3B
shows an expansion of the low binding energy region. The
secondary electron cutoffs and thresholds of the highest occupied
molecular (HOMO) peaks were determined as described in the
literature.16 In the case of the HOMO, the threshold was taken
as the intersection of lines drawn from the leading edge of the
peak and the background. A summary of the results for all of
the polymers is presented in Table 2. Because of uncertainties
in determining the HOMO thresholds and sample-to-sample
variations, we estimate the errors in the ionization energies to
be (0.2 eV, as determined by multiple sample analyses. As
Figure 1. Single-crystal X-ray ORTEP structures of (left) 3-a (50%
probability) and (right) 3-b (30% probability).
vibronic fine structure (Figure 2). The emission of P-3 thin film
exhibits a Stokes shift of 49 nm, which is 3 times larger than
that of P-1. Similarly, large Stokes shifts, defined as the energy
difference between the 0-0 transitions in the absorption and
emission spectra, are also observed for the other fluorinated
polymers relative to their alkoxy counterparts (i.e., P-1 vs P-3,
P-4, P-5 and P-6 vs P-7 and P-8 vs P-10). These results indicate
that the perfluorinated alkyl groups, including simple trifluo-
romethyls, generally produce greater conformational relaxations
in their excited state.
(15) Kim, Y.; Bouffard, J.; Kooi, S.; Swager, T. M. To be published.
(16) (a) Salaneck, W. R.; Stafstro¨m, S.; Bre´das, J.-L. Conjugated Polymer
Surfaces and Interfaces; Cambridge University Press: Cambridge, 1996.
(b) Salaneck, W. R.; Lo¨gdlund, M.; Fahlman, M.; Greczynski, G.; Kugler,
Th. Mater. Sci. Eng. 2001, 121-146. (c) Liao, L.-S.; Lee, C. S.; Lee, S.
T.; Inbasekaran, M.; Wu, W. W. In Conjugated Polymer and Molecular
Interfaces; Salaneck, W. R., Seki, K., Kahn, A., Pireaux, J.-J., Eds; Marcel
Dekker: New York, 2002; pp 401-441.
The optical HOMO-LUMO energy gap (Eg) values were
determined from the energy of the UV-vis absorption edge in
solution. The HOMO-LUMO gaps of PPEs incorporating
perfluoroalkyl groups were only slightly larger than for alkoxy-
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High Ionization Potential Conjugated Polymers
A R T I C L E S
Table 1. Photophysical Data of Polymers
Solution
Film
1
c
λ
λ
max,abs/nm
max,em/nm
Stokes
shift/nmb
λ
λ
max,abs/nm
Stokes
shift/nmb
ꢀmax/M-1 cm-
ΦF
polymer
M
n (PDI)
E
g (eV)a
max,em/nm
(log
ꢀ)
(CHCl3)
P-1
64 kDa
(2.54)
18 kDa
(1.71)
22 kDa
(2.91)
18 kDa
(2.15)
21 kDa
(1.82)
17 kDa
(1.96)
28 kDa
(2.00)
18 kDa
(1.24)
2.65 ( 0.03
2.77 ( 0.03
2.76 ( 0.03
2.77 ( 0.03
2.65 ( 0.03
2.78 ( 0.03
2.66 ( 0.03
2.80 ( 0.03
432
453, 482
395
438, 466
395
440, 467
391
437, 465
436
457, 486
405
432, 459
442
458, 488
390
21
43
45
46
21
27
16
37
449
465, 489
394
443, 472
393
447, 473
387
444, 470
445
464, 496
418
441, 496
443
463, 492
392
16
49
54
57
19
23
20
39
28000
(4.45)
50000
(4.70)
49000
(4.69)
36200
(4.56)
50500
(4.70)
41500
(4.62)
72000
(4.86)
61400
(4.79)
0.67
P-3
P-4
P-5
P-6
P-7
P-8
P-10
0.65
0.55
0.56
0.59
0.87
0.57
0.84
427, 459
431, 459
a The optical HOMO-LUMO energy gap is based on the low energy onset in the UV-vis spectra. b The magnitude of the Stokes shift was calculated
by ∆ ) λmax,em - λmax,abs
.
c Fluorescence quantum yields were determined using quinine sulfate in 0.1 N sulfuric acid (ΦF ) 0.53) as the fluorescence
standard.
Table 2. He I Ultraviolet Photoelectron Spectroscopy Results
cutoff
(eV)a
HOMO
threshold (eV)a
ionization
polymer
potential (eV)
P-1
P-3
P-4
P-5
P-6
P-7
P-8
P-10
17.70
17.08
17.73
17.62
17.68
17.39
17.28
16.63
2.30
2.18
2.30
2.38
2.40
2.57
2.02
2.16
5.82
6.32
5.79
5.98
5.94
6.40
5.96
6.75
a The secondary electron cutoff and HOMO threshold energies are
expressed relative to the spectroscopic Fermi level.
PPE backbone. The perfluoroalkyl substitution in the PPE
system containing the pentiptycene moiety allows for the tuning
of ionization potential by as much as 0.50 eV (P-1 vs P-3).
The order is the following: P-4 (5.79 eV), P-1 (5.82 eV), P-6
(5.94 eV), P-8 (5.96 eV), P-5 (5.98 eV), P-3 (6.32 eV), P-7
(6.40 eV), and P-10 (6.75 eV). On the basis of simple
electronegativity arguments, P-1 would be expected to have the
lowest ionization potential, and this is true within the error of
the experiment.
Figure 2. The absorption and emission spectra of (A) P-1 and (B) P-3 in
chloroform (dotted line) and solid film (solid line).
Photobleaching Studies. We recently reported that perfluo-
roalkyls could impart exceptional resistance to photobleaching
upon irradiation of polymer thin films as compared to nonflu-
orinated polymers.17 The key feature of our system is the high
ionization potential, and in accord, these materials are expected
to have improved photostability. Figure 4 compares the pho-
tobleaching of polymer thin films with the same optical density,
as monitored by fluorescence spectroscopy. The photooxidation
studies were performed by continuous UV irradiation of polymer
thin films using a 450 W Xe lamp as the irradiation source (slit
width ) 10 nm) under aerobic conditions. The percent of
photobleaching was calculated from the loss in fluorescence
intensity at the maximum emission wavelength. As shown in
Figure 4, P-1, which displayed the lowest ionization potential,
retains 50% of its fluorescence intensity after 30 min irradiation
at an excitation wavelength of 380 nm, whereas 85% of the
fluorescence intensity of P-10, the material with the highest
Figure 3. (A) He I ultraviolet photoelectron spectra of P-1, P-3, and P-10
polymer films spin-coated on gold substrates, and (B) expanded graph of
the HOMO threshold region. The arrows indicate the thresholds of the
HOMOs. The binding energy scale is referenced to the spectroscopic Fermi
level.
expected, the P-10 film has the highest ionization potential, with
a value of 6.75 eV, which is 0.79 eV higher than that of P-8
having alkoxy groups instead of perfluoroalkyl groups in the
(17) Kim, Y.; Swager, T. M. Chem. Commun. 2005, 372-374.
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J. AM. CHEM. SOC. VOL. 127, NO. 34, 2005 12125

A R T I C L E S
Kim et al.
Table 3. Stern-Volmer Quenching Constants of Polymers with
Indole in THF
1
polymers
K
sv (M-
)
P-1
P-3
P-5
P-7
P-8
P-10
0.9
11.6
10.5
11.8
1.4
25.6
by P-10 reflects the hyperconjugative and inductive influence
of the electron-poor olefinic portion of the [2.2.2] bicyclic ring
system. The quenching efficiency of P-7 to indole was similar
to that of P-3, and no new absorption or fluorescence peaks
appeared upon addition of excess indole to chloroform solutions
of the polymers. We investigated the response of P-10, which
showed the highest sensitivity to indole, in more detail by
conducting fluorescence lifetime measurements as a function
of quencher concentration. Time-resolved fluorescence measure-
ments indicated that the emission decay of P-10 without
quencher was a single-exponential with a lifetime of 0.40 ns.
With increasing indole concentration, P-10’s lifetime was
shorter, which indicates competitive dynamic quenching (Figure
5). The bimolecular quenching constant (kq) calculated from
the lifetime measurement was 1.4 × 1010 M-1 s-1, implying a
highly diffusion-controlled quenching process.
Figure 4. The fluorescence intensity of polymer thin films after UV
irradiation for 30 min. The optical density of all of the polymer thin films
was 0.1 ( 0.01.
Fluorescence Quenching Study in Polymer Films. We have
also determined the response and characteristics of the polymers
in the solid state, for which they are most likely to be used in
sensing applications. In these studies, we found it useful to
perform two types of determinations. To measure the spectro-
scopic properties and time-dependent quenching profiles, we
performed steady-state quenching experiments with polymer thin
films prepared on glass substrates by spin-coating from chlo-
roform solutions of the polymers. We measured the fluorescence
intensity of polymer thin films as a function of exposure time
to indole vapor (an equilibrium vapor pressure of indole: 1.22
× 10-2 mmHg). In this scheme, the indole reaches the polymer
by slow diffusion, as there is no turbulence, and we can
reproducibly obtain Stern-Volmer plots to determine the
relative performance of our materials. We also performed
measurements using a commercially available system developed
for fluorescence vapor sensing.18 In these sensory systems, the
polymers were coated on the inside of a glass capillary, and
analyte vapor was pulled through the capillary by flow of a
carrier gas. The polymer was maintained at a precise temperature
(40 °C) and was excited at 405 nm using a light-emitting diode.
The luminescence intensity at 435 nm was monitored by a
photodiode. Measurements from this sensor platform revealed
the performance of the polymers under more realistic sensing
conditions.
Figure 5. (A) The fluorescence spectra (λex ) 380 nm) of P-10 as a
function of added indole in THF: [P-10] ) 1.5 × 10-6 M; [indole] )
0-0.135 M (top to bottom). (b) The Stern-Volmer plot and lifetime
measurements of P-10 as a function of added indole in THF.
ionization potential, remain under the same irradiation condi-
tions. This result demonstrates that the higher ionization potential
significantly increases the materials’ resistance to photobleach-
ing.
Steady-State and Time-Resolved Fluorescence Quenching
Studies in Solution. The electron-deficient nature of the
polymers containing perfluoroalkyls directly attached to the
polymer backbone phenyls and their large band gaps make them
powerful excited-state oxidants (electron acceptors). Hence, their
properties are the opposite of typical CP-based sensory materials
that are excited-state reductants (electron donors), and as a
consequence, we expect them to be insensitive to electron-
accepting nitroaromatics, but highly sensitive to readily oxidized
indoles and phenols. To explore their sensory potential, and also
to determine to what degree their sensitivity is related to their
ionization potential, we have conducted quenching studies using
steady-state and time-resolved fluorescence quenching tech-
niques with several electron-donating molecules in solution and
solid state.
We are interested in sensory responses to indole and phenols
due to their biological significance as the aromatic portions of
tryptophan and tyrosine, respectively.9 The change of fluores-
cence intensity of P-10 upon titration with indole and a typical
Stern-Volmer plot are shown in Figure 5. The quenching
efficiencies of all of the polymers were determined by the
Stern-Volmer quenching constants (Ksv) and the values ranged
from 1 to 26 M-1 (Table 3). The Ksv value for P-10 with indole
was 26 M-1, a value 25 times larger than those of the lower
ionization potential polymers P-1 and P-8 and twice that of P-7.
Our fluorescence quenching studies all appear to be in accord
with the polymers’ ionization potentials. The greater quenching
(a) Steady-State Quenching Spectroscopic Studies. To
investigate structural and steric effects on quenching response,
the quenching efficiency of polymer thin films upon exposure
to indole vapor was measured. Figure 6 shows Stern-Volmer
plots of P-1, P-3, P-5, and P-10 as a function of exposure time
to indole vapor. P-10, with the highest ionization potential,
showed the highest quenching efficiency, close to 90% fluo-
rescence quenching after 5 min exposure, followed by P-3 and
(18) These systems are known as Fido sensors and are available from Nomadics
Inc in Stillwater, OK.
9
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High Ionization Potential Conjugated Polymers
A R T I C L E S
and the indole. Interestingly, the exciplex peak is maximal upon
initial exposure to indole, and continued exposure results in a
reduction in the emission intensity.19 Hence, there is competition
between energy transfer to emissive exciplexes and electron-
transfer quenching. This unusual quenching behavior was further
examined by exposing the P-10 film to other analyte vapors
and by investigating absorption and emission spectra of P-10
blend films with electron-donating or -accepting aromatic
molecules.
The emission spectra of P-10 films upon exposure to other
electron-donating analytes, such as dimethyl aniline (DMA),
1,4-dimethoxybenzene (DMB), and N,N-dimethyl-p-toluidine
(DMT), also displayed broad, red-shifted, and structureless peaks
at longer wavelengths, depending on the oxidation potentials
of the analytes (Figure 7B). An exciplex peak was not observed
with electron-accepting analytes, such as 2,4-dinitrotoluene
(DNT). P-7, having similar structure to that of P-10, also showed
an exciplex peak on exposure to electron-donating analytes, but
the peak is not clearly resolved in this case.15
Figure 6. The Stern-Volmer plots of P-1, P-3, P-5, and P-10 in spin-cast
films as a function of exposure time to indole vapor.
(b) Differential Sensory Responses. To best evaluate and
contrast the relative responsiveness of P-1 and P-10 to indole
(an electron-donating analyte) and 2,4-dinitrotoluene (DNT) (an
electron-accepting analyte), we employed a commercially avail-
able system designed to detect chemical vapors.18 With this
system, we can readily sample vapor from the headspace of
equilibrated containers to determine the relative responses of
materials in a reproducible procedure. Simple inspection of the
data shown in Figure 8 reveals the dramatically contrasting
behaviors of P-1 and P-10. Two-second exposure of indole
vapor quenches (50%) the fluorescence from P-10 (Figure 8B),
and this material demonstrates excellent reversibility with an
immediate recovery of the original fluorescence intensity upon
removal of the vapor. In contrast 2 s exposure of P-10 to 2,4-
DNT vapor gives no response other than that associated with
thermal perturbations associated with the sampling. The useful-
ness of P-10’s sensory behavior is best demonstrated by
comparison of the responses of P-1 (Figure 8A), which displays
ultrasensitivity to TNT and 2,4-DNT. When subjected to 2 s
exposures to equilibrium vapors, P-1 exhibited 10% fluorescence
quenching to vapor and 65% fluorescence quenching to 2,4-
DNT. This reciprocal behavior confirms our assertions that the
high ionization materials are key elements to augment the
capabilities of fluorescent-based vapor sensors.
Figure 7. The time-dependent fluorescence spectra of (A) P-10 film before
(dotted line) and after exposure to indole vapor (solid line) at 1 s, 1, 2, 3,
4, 5, 6, 7, and 10 min (top to bottom). (B) The normalized fluorescence
spectra of P-10 films blended with indole, dimethyl aniline (DMA), 1,4-
dimethoxybenzene (DMB), and N,N-dimethyl-p-toluidine (DMT).
then P-5. The stronger quenching of P-3 also suggests that bulky
tert-butyl groups in P-5 prevent efficient diffusion of indole
through the cavity. Meanwhile, relatively electron-rich (pho-
toreducing) P-1, which is known to display efficient sensory
response for TNT,5a exhibited a negligible response to indole
vapor under the same conditions.
Thin films of P-10 displayed the most interesting responses
to indole vapor and initially displayed rapid decreases in the
427 and 465 nm emission bands, with the appearance of an
intense broad, featureless peak at 496 nm, as shown in Figure
7A. The excitation or absorption spectra of the P-10 film did
not show the appearance of the longer wavelength absorption
band in the presence or absence of analytes, which indicates
that the new broad band centered at 496 nm does not originate
from a ground-state charge-transfer complex. We therefore
attribute this long wavelength emission band to an exciplex
(excited-state charge complex) between the excited state of P-10
Figure 8. Plot of changes in fluorescence intensity of (A) P-1 and (B) P-10 film exposed to indole (blue solid) and 2,4-DNT (red dot) vapors for the
indicated time.
9
J. AM. CHEM. SOC. VOL. 127, NO. 34, 2005 12127

A R T I C L E S
Kim et al.
and then subjected to a CHCl3/H2O workup. The solvent was removed,
and the resulting solid was collected by filtration. The crude solid was
dissolved in 50 mL of acetone, and then a solution of tin(II) chloride
dihydrate (9.2 g, 40.5 mmol) in 50% acetic acid (50 mL) was added
dropwise. This mixture was stirred at room temperature for 24 h. The
resulting blue solid product was filtered. The solid was then dissolved
in hexane, washed with water and saturated sodium bicarbonate solution,
and then dried over magnesium sulfate. The hexane solution is then
poured onto a silica plug, which is flushed with hexane (200 mL),
followed by 9:1 hexane/methylene chloride to elute a deep blue solid
Conclusion
We have synthesized new electron-deficient PPE derivatives
containing perfluoroalkyl groups and determined that tuning of
their ionization potentials (verified by UPS) can be used to
impart dramatic selectivity changes in sensory responses.
Sensing of electron-donating analytes by high ionization
potential polymers was demonstrated by fluorescence quenching
studies. Excited-state charge-transfer complexes (exciplexes)
observed for P-7 and P-10 films suggest prospects for new
sensory schemes based upon the detection of exciplex emission.
1
(9.5 g, 92%): mp 220-221 °C; H NMR (300 MHz, CDCl3) δ 9.31
(s, 4H), 7.98 (dd, J ) 6.6 and 3.0 Hz, 4H), 7.42 (dd, J ) 6.6 and 3.0
Hz, 4H), 1.39 (s, 42H); HR-MS (EI) calcd for C44H54Si2 (M+) 638.38,
found 638.37. (lit.20 mp 210 °C).
Experimental Section
General Methods. NMR (1H, 13C, and 19F) spectra were recorded
6,13-Bis(triisopropylsilylethynyl)-5,7,12,14-tetrahydro-5,7,12,14-
(1′,2′-tetra(carbomethoxy))ethenopentacene (2-a). To a solution of
1 (1.00 g, 1.57 mmol) in 40 mL of xylene in a sealed vessel was added
dimethylacetylenedicarboxylate (1.93 mL, 15.7 mmol) at room tem-
perature and stirred at 140 °C for 48 h. The mixture was allowed to
cool to room temperature, and the reaction solvent was removed under
vacuum to give solid residues. The crude mixture was purified by silica
column chromatography using 20% EtOAc in hexane as eluent to give
a pure mixture of two isomers (syn and anti) (1.3 g, 90%). The two
isomers were separated by their solubility difference. Recrystallization
using hexane gave the anti-isomer as a white solid (0.58 g, 40%).
Further silica column chromatography (10% EtOAc in hexane) of the
supernatant gave the syn-isomer as a white solid (0.55 g, 38%): 2-a-
on Varian Mercury 300 MHz or Bruker Advance 400 MHz spectrom-
1
eters. The H and 13C chemical shifts are given in units of δ (ppm)
relative to tetramethylsilane (TMS) where δ (TMS) ) 0, and referenced
to the residual solvent. 19F NMR chemical shifts are reported relative
to trichlorofluoromethane as the reference. Melting point determinations
were performed using a Laboratory Devices MEL-TEMP instrument
(open capillaries used) and were uncorrected. High-resolution mass
spectra were obtained with a Finnigan MAT 8200 system using sector
double focus and an electron impact source with an ionizing voltage
of 70 V. The X-ray crystal structure was determined with a Siemens
SMART/CCD diffractometer. The molecular weights of polymers were
determined using a PLgel 5 µm Mixed-C (300 × 7.5 mm) column and
a diode detector at 254 nm at a flow rate of 1.0 mL/min in THF. The
molecular weights are reported relative to polystyrene standards
purchased from Polysciences, Inc. Polymer thin films deposited on a
cover glass (18 mm × 18 mm) were prepared by spin casting using an
EC101DT photo resist spinner (Headway Research, Inc.) from chlo-
roform solutions of the polymers. The film thickness was determined
for samples prepared on cover glasses using a profilometer (Veeco
Dektak 6M). Samples for fluorescence quenching and photobleaching
studies were prepared by spin-coating from chloroform solutions (1
mg/mL) at a rate of 3000 rpm. The same concentration was used to
obtain polymer-coated glass capillaries for the Fido measurements. For
these experiments, the capillary is attached to the spin-coater platform,
and a spin rate of 1000 rpm drives the polymer solution through the
capillary. For UPS studies, solutions of 4 mg of polymer in 1 mL of
chloroform were spin-coated to generate films (ca. 100-300 Å) on
gold surfaces at a spin rate of 3000 rpm.
Materials. All solvents were spectral grade unless otherwise noted.
Anhydrous THF, xylene, DMSO, toluene, and diisopropylamine were
purchased from Aldrich Chemical Co., Inc. All other compounds were
purchased from Aldrich and used as received. All air- and moisture-
sensitive synthetic manipulations were performed under an argon
atmosphere using standard Schlenk techniques. Silica gel (40 µm) was
obtained from J. T. Baker.
6,13-Bis(triisopropylsilylethynyl)pentacene (1). This procedure is
an adaptation of that reported by Anthony et al.19 Under an atmosphere
of argon, 16.2 mL of n-butyllithium (40.5 mmol, 2.5 M solution in
hexane) was added dropwise to 9.1 mL (40.5 mmol) of triisopropylsilyl
acetylene in 50 mL of dry tetrahydrofuran at 0 °C. The mixture was
kept at 0 °C for another 40 min before it was transferred to a solution
of 6,13-pentacenequinone (5 g, 16.2 mmol) in 50 mL of dry tetrahy-
drofuran at 0 °C. The mixture was warmed to room temperature and
stirred overnight. The reaction was quenched with 15 mL of 10% HCl
1
syn; mp > 300 °C; H NMR (300 MHz, CDCl3) δ 7.27 (dd, J ) 5.4
and 3.0 Hz, 4H), 6.97 (dd, J ) 5.4 and 3.0 Hz, 4H), 5.90 (s, 4H), 3.79
(s, 12H), 1.29 (s, 42H); 13C NMR (75 MHz, CDCl3) δ 165.6, 147.7,
143.6, 143.5, 125.8, 124.2, 115.5, 101.1, 99.7, 52.6, 51.2, 19.0, 11.6;
HR-MS (EI) calcd for C56H66O8Si2 (M+) 922.4291, found 922.4263.
2-a-anti: mp > 300 °C; 1H NMR (300 MHz, CDCl3) δ 7.33 (dd, J )
5.4 and 3.0 Hz, 4H), 7.04 (dd, J ) 5.4 and 3.0 Hz, 4H), 5.89 (s, 4H),
3.73 (s, 12H), 1.29 (s, 42H); 13C NMR (75 MHz, CDCl3) δ 165.5,
147.7, 143.6, 143.5, 125.9, 124.3, 115.5, 101.1, 99.7, 52.6, 51.1, 19.1,
11.6; HR-MS (EI) calcd for C56H66O8Si2 (M+) 922.4291, found
922.4263.
6,13-Bis(triisopropylsilylethynyl)-5,7,12,14-tetrahydro-5,7,12,14-
(1′,2′-tetra(trifluoromethyl))ethenopentacene (2-b). Hexafluoro-2-
butyne (1.52 g, 9.39 mmol) was condensed in a 60 mL pressure tube
by a dry ice/acetone cooling bath. A solution of 1 (2 g, 3.13 mmol) in
xylene (10 mL) was slowly added through a septum. The pressure tube
was then capped and heated in a 100 °C oil bath for 24 h. After being
cooled to room temperature, the reaction mixture was concentrated in
vacuo, and the residue was crystallized from hexane. The white
crystalline material was collected by filtration and dried (1.7 g) to give
2-b-anti as the major isomer. The mother liquor was concentrated and
purified by silica column chromatography using 30% EtOAc in hexane
as eluent to give a second batch of 2-b-syn (0.8 g). Total yield: 83%.
2-b-syn: mp > 300 °C; 1H NMR (300 MHz, CDCl3) δ 7.31 (dd, J )
5.4 and 3.3 Hz, 4H), 7.04 (dd, J ) 5.4 and 3.3 Hz, 4H), 5.92 (s, 4H),
1.28 (s, 42H); 19F NMR (282 MHz, CDCl3) δ -61.7; HR-MS (EI)
calcd for C52H54F12Si2 (M+) 962.3571, found 962.3421. 2-b-anti: mp
1
> 300 °C; H NMR (300 MHz, CDCl3) δ 7.41 (dd, J ) 5.4 and 3.3
Hz, 4H), 7.14 (dd, J ) 5.4 and 3.3 Hz, 4H), 5.92 (s, 4H), 1.28 (s,
42H); 19F NMR (282 MHz, CDCl3) δ -61.8; HR-MS (EI) calcd for
C52H54F12Si2 (M+) 962.3571, found 962.3421.
Compound 3-a. Tetrabutylammonium fluoride (1 M in THF; 0.015
mL, 0.146 mmol) was added to a stirred solution of 2-a-anti (45 mg,
0.049 mmol) in THF (3 mL) at room temperature. The mixture was
allowed to stir for 30 min at this temperature. The reaction mixture
was concentrated in vacuo, and the residue was passed through a short
plug of silica. The crude product was crystallized from hexane and
dichloromethane (10:1) to give 3-a-anti as a white solid (27.5 mg, 92%).
3-a-anti: mp > 300 °C; 1H NMR (300 MHz, CDCl3) δ 7.42 (dd, J )
(19) The lifetimes of P-10 film are 0.17 ns at 427 nm without indole and 4.5 ns
at 496 nm with indole. The long lifetime of this new emission peak
confirmed that it originated from exciplex emission.
(20) Melhuish, W. H. J. Phys. Chem. 1961, 65, 229.
(21) (a) Anthony, J. E.; Brooks, J. S.; Eaton, D. L.; Parkin, S. R. J. Am. Chem.
Soc. 2001, 123, 9482-9483. (b) Osaheni, J. A.; Jenekhe, S. A. J. Am. Chem.
Soc. 1995, 117, 7389.
(22) Handbook of Physical Properties of Organic Chemicals; Howard, P. H.,
Meylan, W. M., Eds.; CRC Press: Boca Raton, FL, 1997.
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High Ionization Potential Conjugated Polymers
A R T I C L E S
5.4 and 3.3 Hz, 4H), 7.05 (dd, J ) 5.4 and 3.3 Hz, 4H), 5.89 (s, 4H),
3.75 (s, 12H), 3.67 (s, 2H); 13C NMR (75 MHz, CDCl3) δ 165.8, 147.2,
144.1, 143.4, 126.0, 124.4, 114.7, 85.7, 77.8, 52.7, 50.9; HR-MS (ESI)
calcd for C38H26O8 ([M + Na]+) 633.1520, found 633.1520.
3-a-syn was prepared by using 2-a-syn in a similar procedure as
3-a-anti. 3-a-syn: mp > 300 °C; 1H NMR (300 MHz, CDCl3) δ 7.37
(dd, J ) 5.4 and 3.0 Hz, 4H), 6.99 (dd, J ) 5.4 and 3.0 Hz, 4H), 5.89
(s, 4H), 3.81 (s, 12H), 3.67 (s, 2H); 13C NMR (75 MHz, CDCl3) δ
165.8, 147.2, 144.1, 143.4, 125.9, 124.4, 114.7, 85.7, 77.8, 52.8, 50.9;
HR-MS (ESI) calcd for C38H26O8 ([M + Na]+) 633.1520, found
633.1513.
Polymers 1-10. A general procedure is illustrated by the synthesis
of polymer 10. Compound 3-b (27.8 mg, 0.043 mmol), compound 6
(30 mg, 0.042 mmol), CuI (0.47 mg, 0.003 mmol), and Pd(PPh3)4 (4.8
mg, 0.0042 mmol) were placed in a 25 mL Schlenk tube with a stir
bar. The flask was evacuated and back-filled with argon three times,
followed by the addition of degassed diisopropylamine/toluene (1:2,
4.5 mL) under an atmosphere of argon. This mixture was heated at 70
°C for 3 days and then subjected to a CHCl3/H2O workup. The
combined organic phase was washed with 10% NH4Cl and then dried
(MgSO4). The solvent was removed in vacuo, and the residue dissolved
in chloroform was reprecipitated in methanol. The resulting precipitate
was filtered and washed with MeOH and acetone to give a yellow solid
(35 mg, 69%). Removal of oligomer and impurities was achieved by
subjecting the solid to sequential extractions in a Soxhlet apparatus
with MeOH, acetone, followed with chloroform. The chloroform
fraction was characterized. P-3 (69%): 1H NMR (400 MHz, CDCl3) δ
8.6-8.5 (br, 1H), 8.4-8.3 (br, 1H), 7.6-7.4 (br, 8H), 7.2-7.0 (br,
8H), 6.1-6.0 (br, 2H), 5.9-5.8 (br, 2H). P-4 (82%): 1H NMR (300
MHz, CDCl3) δ 8.5-8.4 (br, 2H), 7.6-7.4 (br, 8H), 7.2-7.0 (br, 4H),
6.1-5.9 (br, 4H), 1.4-1.2 (br, 36H). P-5 (%): 1H NMR (400 MHz,
CDCl3) δ 8.5-8.3 (br, 2H), 7.6-7.3 (br, 8H), 7.2-7.0 (br, 4H), 6.1-
5.7 (br, 4H), 1.4-1.2 (br, 36H). P-6 (71%): 1H NMR (300 MHz,
CDCl3) δ 7.6-7.5 (br, 4H), 7.4-7.3 (br, 2H), 7.2-7.0 (br, 4H), 6.2-
6.1 (br, 4H), 4.4-4.3 (br, 4H), 3.8-3.7 (br, 12H), 2.2-2.0 (br, 4H),
1.7-1.5 (br, 8H), 1.4-1.2 (br, 28H), 0.9-0.8 (br, 6H). P-7 (65%):
1H NMR (300 MHz, CDCl3) δ 8.5-8.4 (br, 1H), 8.3-8.2 (br, 1H),
7.6-7.4 (br, 4H), 7.2-7.0 (br, 4H), 6.2-5.9 (br, 4H), 3.9-3.6 (br,
12H). P-8 (74%): 1H NMR (300 MHz, CDCl3) δ 7.7-7.6 (br, 4H),
7.6-7.4 (br, 2H), 7.2-7.0 (br, 4H), 6.2-6.0 (br, 4H), 4.4-4.2 (br,
4H), 2.2-2.0 (br, 4H), 1.7-1.5 (br, 4H), 1.5-1.4 (br, 4H), 1.4-1.2
(br, 28H), 0.9-0.8 (br, 6H). P-10 (69%): 1H NMR (300 MHz, THF-
d8) δ 8.6-8.5 (br, 1H), 8.5-8.4 (br, 1H), 7.7-7.5 (br, 4H), 7.3-7.0
(br, 4H), 6.2-6.0 (br, 4H).
Photophysical Methods. UV-vis spectra were obtained from
Hewlett-Packard 8452A diode array or Cary 50 UV-visible spectro-
photometers. Fluorescence studies were conducted with a SPEX
Fluorolog-τ2 fluorometer (model FL112, 450 W xenon lamp) equipped
with a model 1935B polarization kit. The spectra in solution were
obtained at 25 °C using a quartz cuvette with a path length of 1 cm.
Polymer thin film spectra were recorded by front-face (22.5°) detection.
Fluorescence quantum yields of polymers in CHCl3 solution were
determined relative to equiabsorbing solutions of quinine sulfate (ΦF
) 0.53 in 0.1 N sulfuric acid).21 The solid-state quantum yields were
obtained relative to 10-3 M 9,10-diphenylanthracene in poly(methyl
methacrylate) (PMMA) (ΦF ) 0.83) as a reference.20 The time decay
of fluorescence was determined by a phase-modulation method, using
frequencies from 10 to 300 MHz.
Compound 3-b. Tetrabutylammonium fluoride (1 M in THF; 1.56
mL, 1.56 mmol) was added to a stirred mixture of both isomers of 2-b
(500 mg, 0.52 mmol) in THF (20 mL) at room temperature. The mixture
was allowed to stir for 30 min at this temperature. The reaction mixture
was concentrated in vacuo, and the residue was passed through a short
plug of silica. The crude product was concentrated and purified by silica
column chromatography (10% EtOAc in hexane) to give 3-b as a white
solid mixture of two isomers (283 mg, 84%). 3-b-anti: mp > 300 °C;
1H NMR (300 MHz, CDCl3) δ 7.50 (dd, J ) 5.4 and 3.3 Hz, 4H), 7.15
(dd, J ) 5.4 and 3.3 Hz, 4H), 5.89 (s, 4H), 3.76 (s, 2H); 19F NMR
(282 MHz, CDCl3) δ -61.9; HR-MS (EI) calcd for C34H14F12 (M+)
1
650.09, found 650.09. 3-b-syn: mp > 300 °C; H NMR (300 MHz,
CDCl3) δ 7.41 (dd, J ) 5.4 and 3.3 Hz, 4H), 7.06 (dd, J ) 5.4 and 3.3
Hz, 4H), 5.89 (s, 4H), 3.76 (s, 2H); 19F NMR (282 MHz, CDCl3) δ
-61.7; HR-MS (MALDI) calcd for C34H14F12 ([M + H]+) 651.0977,
found 651.1009.
2,5-Diiodo-1,4-bis(trifluoromethyl)benzene (4). To a solution of
30 mL of H2SO4 were added periodic acid (3.18 g, 14 mmol) and
potassium iodide (6.90 g, 42 mmol) at 0 °C, and then 1,4-bis-
(trifluoromethyl)benzene (2.17 mL, 14 mmol) was added. The reaction
mixture was then stirred at 75 °C for 5 h. After cooling to room
temperature, the resulting solution was poured into ice-water and then
extracted with diethyl ether (100 mL) and 10% sodium thiosulfate (50
mL). The organic layer was washed with 10% sodium thiosulfate (3 ×
50 mL), dried over MgSO4, filtered, and concentrated. The residue was
recrystallized from hexane to give 4 as a white solid (4.24 g, 65%):
mp 118-119 °C; 1H NMR (300 MHz, CDCl3) δ 8.20 (s, 2H); 19F NMR
(282 MHz, CDCl3) δ -64.2; HR-MS (EI) calcd for C8H2F6I2 (M+)
465.8145, found 465.8159.
4-(Perfluorooctyl)-r,r,r-trifluorotoluene (5). A C8F17I (12 g, 22
mmol) was added dropwise over 10 min to a stirred mixture of
4-iodobenzotrifluoride (3 g, 11 mmol), copper powder (5.6 g, 88 mmol),
2,2′-bipyridine (120 mg, 0.8 mmol), and DMSO (30 mL) at 70 °C.
The reaction mixture was subsequently stirred for a further 72 h at this
temperature. After cooling to room temperature, the mixture was poured
into a beaker containing ether (100 mL) and water (100 mL). After
filtering, the organic layer was separated, washed with water (3 × 50
mL), and dried over MgSO4. Sublimation under vacuum gave the
product 5 as a white solid (5.6 g, 90%): mp 48-50 °C; 1H NMR (300
MHz, CDCl3) δ 7.77 (dd, J ) 8.1 and 8.4 Hz, 4H); 19F NMR (282
MHz, CDCl3) δ -64.0, -81.4, -111.6, -121.4, -122.0, -122.1,
-122, 9, -126, 3; HR-MS (EI) calcd for C15H4F20 (M+) 563.9988,
found (M+) 563.9996.
Fluorescence Quenching Studies. Fluorescence quenching and
absorption experiments in solution were carried out by microtitration
in a fluorescence cuvette. In a typical titration quenching experiment,
2.5 mL of polymer solution was placed in a 1 cm quartz fluorescence
cell. The UV-visible absorption and fluorescence spectra were recorded
at room temperature. Then absorption and fluorescence spectra were
repeatedly acquired after the addition of microliter aliquots of a polymer
solution that contained the quencher. The fluorescence quenching
studies of polymer films were performed following the literature
procedure.11 The fluorescence spectra were recorded immediately after
exposing the polymer films to the vapor of analyte for a specific period
of time at an excitation wavelength of 380 nm. The equilibrium vapor
pressures of the analyte are assumed to be similar to the documented
values.22
1-Perfluorooctyl-4-trifluoromethyl-2,5-dibromobenzene (6). Into
a 500 mL round-bottom flask were placed 120 mL of trifluoroacetic
acid, compound 5 (12 g, 21.3 mmol), and 36 mL of sulfuric acid (98%).
The mixture was stirred vigorously, and NBS (11.4 g, 63.8 mmol) was
added in portions at 60 °C over 5 h period. After stirring at 60 °C for
2 days, the mixture was poured into 200 mL of ice-water. The
precipitates were filtered and sublimed to give a white solid 6 (13.5 g,
Photoelectron Spectroscopy. The samples for ultraviolet photo-
electron spectroscopy (UPS) measurements were prepared by spin-
coating polymer solutions in chloroform (4 mg/mL) onto gold substrates
at a rate of 3000 rpm for 60 s. The gold substrates were prepared by
thermally depositing approximately 2000 Å of gold on ca. 1 cm2 pieces
1
88%): mp 53-54 °C; H NMR (300 MHz, CDCl3) δ 8.04 (s, 1H),
7.92 (s, 1H); 19F NMR (282 MHz, CDCl3) δ -64.2, -81.3, -108.0,
-119.8, -121.9, -122.3, -123.2, -126.6; HR-MS (EI) calcd for
C15H2F20Br2 (M+) 719.8198, found (M+) 719.8221.
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A R T I C L E S
Kim et al.
of Si(111) wafers. The polymer-coated gold substrates were attached
to metal sample stubs using vacuum-compatible silver paint, and this
was also used to electrically connect the edges of the samples to the
sample stubs. The UPS experiments were performed in a VG ES-
CALAB MKII photoelectron spectrometer having a base pressure of 1
× 10-9 mbar. A differentially pumped He I lamp emitting 21.22 eV
radiation was used as the excitation source, and photoelectrons were
detected normal to the sample plane by a concentric hemispherical
analyzer operating with a pass energy of 2 eV. During UPS measure-
ments, the sample stub (and sample) was biased -6.32 V relative to
ground, enabling the low kinetic energy portion of the spectrum to be
measured. The work function of the sample was calculated as the
difference between the photon energy (21.22 eV) and the spectrum
width, with the latter determined by measuring the secondary electron
cutoff on the low kinetic energy side of the spectrum and the edge of
the highest occupied molecular orbital (HOMO) on the high kinetic
energy side.
Acknowledgment. This research was supported by the U.S.
Army through the Institute for Soldier Nanotechnologies, under
Contract DAAD-19-02-D-0002 with the U.S. Army Research
Office.
Supporting Information Available: X-ray crystallographic
details of compounds 3-a and 3-b. This material is available
free of charge via the Internet at http://pubs.acs.org.
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12130 J. AM. CHEM. SOC. VOL. 127, NO. 34, 2005