Tunable fluorescent/phosphorescent platinum(II) porphyrin-fluorene copolymers for ratiometric dual emissive oxygen sensing

Article abstract of DOI:10.1021/ic300040n

A series of new platinum(II) 5,15-bis(pentafluorophenyl)-10,20-bis(phenyl) porphyrin-9,9-dioctylfluorene copolymers, in which the relative intensities of the blue fluorescence and red phosphorescence can be easily tuned by the initial feed ratio of the two monomers or energy transfer between the fluorescent and phosphorescent units, have been designed and prepared for the application in ratiometric dual emissive oxygen sensing. To the best of our knowledge, this is the first example of a ratiometric oxygen sensor based on dual fluorescent/phosphorescent polymers or copolymers containing transition-metal complexes. It also provides an alternative and easy way to achieve dual emissive oxygen sensing.

Full text of DOI:10.1021/ic300040n

Article
pubs.acs.org/IC
Tunable Fluorescent/Phosphorescent Platinum(II) Porphyrin−
Fluorene Copolymers for Ratiometric Dual Emissive Oxygen Sensing
Haifeng Xiang,* Li Zhou, Yan Feng, Jinghui Cheng, Di Wu, and Xiangge Zhou*
Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610041, People's Republic of China
S
* Supporting Information
ABSTRACT: A series of new platinum(II) 5,15-bis-
(pentafluorophenyl)-10,20-bis(phenyl)porphyrin−9,9-dioctyl-
fluorene copolymers, in which the relative intensities of the
blue fluorescence and red phosphorescence can be easily tuned
by the initial feed ratio of the two monomers or energy
transfer between the fluorescent and phosphorescent units,
have been designed and prepared for the application in
ratiometric dual emissive oxygen sensing. To the best of our knowledge, this is the first example of a ratiometric oxygen sensor
based on dual fluorescent/phosphorescent polymers or copolymers containing transition-metal complexes. It also provides an
alternative and easy way to achieve dual emissive oxygen sensing.
fluorescence; as a result, no phosphorescence can be observed.
Conversely, an efficient ISC will eliminate the fluorescence and
only phosphorescence can be observed. Only those lumino-
phores with moderate ISC effects can display the fluorescence
and phosphorescence dual emission.9g However, this is not a
problem for the copolymers containing transition-metal
complexes, because the relative intensities of the fluorescence
and phosphorescence can be easily tuned by modifying the
composition of the phosphorescent transition-metal complex
monomer and fluorescent monomer in the polymer.4b,c,e,f
Polyfluorenes (PFO) are an important class of blue
fluorescent conjugated polymers for optoelectronic devices,1
owing to their good solubility, processability, and photophysical
properties. Previously, we reported the applications of [meso-
tetrakis(pentafluorophenyl)porphyrinato]platinum(II) in light-
emitting diodes.10 This fluorinated Pt(II) porphyrin is highly
soluble and stable toward oxidative deterioration and photo-
degradation. Herein, the synthesis and photophysical properties
of poly([5,15-bis(pentafluorophenyl)-10,20-bis(phenyl)-
porphyrinato]platinum(II)−9,9-dioctylfluorene] copolymers
PtP1−PtP3 (Figure 1) are described. The relative intensities
of the fluorescence and phosphorescence of copolymers can be
easily tuned by the initial feed ratio of two monomers, which
are suitable for ratiometric dual emissive oxygen sensing. To
the best of our knowledge, there are a number of examples of
ratiometric oxygen sensing based on dual fluorescent/
phosphorescent molecules, but ratiometric oxygen sensors
based on dual fluorescent/phosphorescent polymers or
copolymers containing transition-metal complexes are still
rare, despite the fact that they are widely used in optoelectronic
devices.1d,4
INTRODUCTION
■
Conjugated polymers have been received great attention in a
variety of applications, such as optoelectronic devices,1
sensors,2 and biomedical applications.2,3 However, these π-
conjugated polymers mainly are fluorescent materials, whose
fluorescence is generated from excited singlet state. One of the
most attractive systems is that of conjugated-polymer-
containing phosphorescent transition-metal complexes. As a
result, by introduction of phosphorescent transition-metal
complexes into π-conjugated polymers, it is possible to tune
the photosensitivity, charge transport, absorption, and
luminescence of the polymers.4
Since the determination of oxygen concentration in solution
is essential for a variety of applications ranging from life
sciences to environmental sciences, optical sensing of oxygen
concentrations has attracted a great deal of scientific attention.5
Intensely phosphorescent transition-metal complexes such as
Pt(II) porphyrin and Ru(II) polypyridyl complexes5 exhibit
very desirable features in terms of their optical spectra, excited-
state lifetimes, luminescence quantum yields, and high stability,
for the purpose of oxygen sensing,6 because the ground state of
O2 is the triplet state and can quench the triplet
phosphorescence. Moreover, ratiometric O2 sensors are more
desired, due to their advantages of eliminating photobleaching
and excitation power fluctuation.7 Usually, most of the reported
ratiometric O2 sensors adopted the method of mixing two
different dyes,8 whose applications were limited by disadvan-
tages, including unequal stability, reliability, and photobleaching
of the two different dyes. Another more efficient way to achieve
ratiometric O2 sensors is to design and synthesize unilumino-
phores9 with dual fluorescence/phosphorescence emission, but
it is difficult to design such dual fluorescent/phosphorescent
luminophores from a photophysical perspective because a
delicate balance between the S1 and T1 excited states has to be
kept. Nonefficient intersystem crossing (ISC) will lead to
Received: January 13, 2012
Published: April 24, 2012
© 2012 American Chemical Society
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Figure 1. Synthetic route of the monomers and the polymers.
RESULTS AND DISCUSSION
Table 1. Results of the Polymers
■
a
b
The polymers PFO and PtP1−PtP3 (Figure 1) were prepared
through Yamamoto coupling between various platinum(II)
5,15-bis(pentafluorophenyl)-10,20-bis(4-bromophenyl)-
porphyrin complexes and 2,7-dibromo-9,9-dioctylfluorene (see
the Experimental Section), as shown in Figure 1. Pentafluor-
ophenyl groups in the Pt(II) porphyrin complex can increase its
solubility and stability.10 Introduction of the 9,9-dioctylfluorene
group improves its solubility and reduces aggregation and steric
hindrance between the Pt(II) porphyrin units. However, PtP4
could not be prepared by this method due to steric hindrance,
which disturbed the formation of an extended π-conjugated
system, when the porphyrin units were directly bonded to form
the polymer.11 The level of Pt(II) porphyrin incorporation into
the final copolymers may be quite different from the initial feed
feed /
NMR /
Mw/
mol %
mol %
yield/% 10−4Mn 10−4Mw
Mn
PFO
PtP1
PtP2
PtP3
0
5.0
20
50
0
72
52
40
28
4.06
3.14
2.67
2.14
6.82
3.92
5.75
1.68
1.45
2.15
3.67
c
8.5
20
7.86
b
a
mol % of monomer Pt(II) porphyrin from feed ratio. mol % of
c
1
Pt(II) porphyrin units calculated by H NMR. No value obtained,
since the signal for Pt(II) porphyrin units was too weak.
Soret bands of Pt(II) porphyrin and fluorene units) at λmax 394
nm and two broad absorption peaks at 510 and 542 nm
corresponding to Q(1,0) and Q(0,0) of the Pt(II) porphyrin
moiety (Figure 2). An increase in the concentration of Pt(II)
porphyrin moieties in the polymers led to slight shifting of the
λmax value of the near-UV band from 394 nm in PtP1 to 400
nm in PtP3.
The photoluminescence (PL) spectra (excited at 375 nm) of
PtP1−PtP3 in degassed CH2Cl2 at room temperature are
depicted in Figure 2. PtP1−PtP3 show blue fluorescence
(emission decay lifetime, τ < 100 ns) attributed to the π−π*
emission of the fluorene ring, as well as the red phosphor-
escence of Pt(II) porphyrin moieties. The relative intensities of
the fluorescence and phosphorescence of copolymers can be
1
ratios and was measured by H NMR analysis (Table 1 and
Figure S1 in the Supporting Information). All the polymers
have good thermal stability, with thermogravimetry analysis
temperatures of 418−422 °C.
The photophysical properties of PFO and PtP1−PtP3 are
summarized in Table 2. The UV/vis absorption of PFO
consists of a strong featureless π−π* transition centered at 376
nm (3.2 eV) that has a relatively broad bandwidth (half-
bandwidth 60 nm), consistent with previous reports on
polyfluorenes.1 PtP1 exhibits a near-UV band (the mixture of
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Table 2. Optical Data of the Polymers
b
absorption in CH2Cl2/nm
PL in CH2Cl2/nm (lifetime/μs)
absorption in thin film/nm
PL in thin film/nm
435, 462, 494, 528
Φ in CH2Cl2/%
a
PFO
PtP1
PtP2
PtP3
376
415, 436, 468
378
70
62
14
7.0
376, 394 510, 542
378, 396, 509, 541
380, 400, 510, 542
416, 439, 469, 652 (45), 713 (44)
416, 439, 470, 654 (51), 714 (49)
416, 438, 468, 655 (40), 715 (39)
378, 399, 512, 540
379, 401, 511, 541
381, 406, 512, 543
437, 465, 498, 531, 652, 719
436, 464, 498, 533, 654, 720
438, 656, 720
a
b
Lifetime of fluorene units <100 ns. With quinine sulfate (Φ = 0.55, quinine in 0.05 mol dm−3 sulfate) as the standard.
Figure 3. PL spectra of PtP3 in 1,2-dichloroethane at room
temperature at various oxygen concentrations.
the red phosphorescence intensities grow with decreasing
oxygen contents, which is in agreement with the reported data
based on Pt(II) porphyrin complexes.5 The color of the
emission changes from blue to red with decreasing oxygen
content and could be seen by the naked eye under UV
excitation.
The oxygen quenching of red phosphorescence intensity at
655 nm in PtP3 can be interpreted in terms of the Stern−
Volmer relation (IP0/IP = 1 + KSV [O2]; where IP0 and IP are
phosphorescence intensities in the absence and in the presence
of oxygen, respectively, [O2] is the concentration of oxygen,
and KSV is the Stern−Volmer quenching constant), as shown in
Figure 4. A good linearity (correlation coefficient R2 = 0.997, n
= 7) of IP0/IP as the function of the concentration of O2
between 0 and 100% is established. The calculated KSV value is
found to be 402 12 bar−1. In order to achieve ratiometric
dual emissive oxygen sensing, the relationship between IF/IP (IF
is blue fluorescence intensity at 416 nm) and oxygen
concentration is depicted in Figure 4. A good linearity (R2 =
Figure 2. Absorption (top) and PL spectra (bottom) of PFO and
PtP1−PtP3 in CH2Cl2.
easily tuned by the initial feed ratio of the two monomers. The
PL of PtP1 is dominated by fluorescence; on the other hand,
the PL of PtP3 is dominated by phosphorescence. In
additional, there is a spectral overlap between the absorption
spectrum of Pt(II) porphyrin monomer (λmax ∼ 400 nm)
(Figure S2, Supporting Information) and PL spectrum of PFO
(λmax ∼415 nm), which provides a possibility of energy transfer
from fluorene units to Pt(II) porphyrin units in the copolymers.
At a Pt(II) porphyrin moiety concentration of 20 mol %
(calculated by 1H NMR), there was a small blue emission from
fluorene units in PtP3, indicating a good energy transfer from
fluorene units to Pt(II) porphyrin units. Long emission decay
lifetimes of the excited state of Pt(II) porphyrin units were
founded to be 39−51 μs in PtP1−PtP3 (Table 2), indicating
their triplet transition nature. All the polymers have bright PL
in degassed CH2Cl2 with quantum yields (Φ) of 0.70, 0.62,
0.14, and 0.070 for PFO and PtP1−PtP3, respectively.
The PL spectra (excited at 375 nm) of PtP3 in 1,2-
dichloroethane at room temperature under various oxygen
concentrations are shown in Figure 3. Under an atmosphere of
100% oxygen, PtP3 produces blue fluorescence with weak red
phosphorescence. The blue fluorescence intensities show little
change with decreasing oxygen contents, but at the same time,
Figure 4. Stern−Volmer plot (black line) and linear correlation
between the ratiometric fluorescent/phosphorescent response toward
O2 partial pressure (red line) of PtP3.
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was stirred at room temperature for an additional 1 h, and then the
solvent was removed. Column chromatography (silica, 1/2 CH2Cl2/
hexane v/v) afforded the porphyrin as the first moving band. Removal
of the solvent under vacuum gave 0.728 g of 5,15-free base porphyrin
as a purple solid (yield 31%). 1H NMR (300 MHz, CDCl3): δ (ppm)
8.97−8.80 (dd, 8 H), 8.07 (m, 4 H), 7.94 (m, 4 H), −2.87 (br s, 2 H).
MS (FAB): calcd for C44H18N4F10Br2 952.45, Found: 952.89. Anal.
Calcd: C, 55.49; H, 1.90; N, 5.88. Found: C, 55.68; H, 2.02; N, 5.81.
UV−vis absorption: 413, 508, 586 nm (CH2Cl2); 418, 512, 589 nm
(thin film). Photoluminescence (fluorescence): 655, 709 nm
(CH2Cl2); 642, 708 nm (thin film).
0.997) is also found. Thin films of the polymers, prepared by
the spin-coating method, have optical properties similar to
those of polymer solutions (Figure S3, Supporting Informa-
tion). Ratiometric dual emissive oxygen sensing based on the
thin films of polymers is now under way.
CONCLUSIONS
■
In conclusion, we have demonstrated a ratiometric dual
emissive oxygen sensing system based on fluorescent/
phosphorescent platinum(II) porphyrin−fluorene copolymers
with only one excitation wavelength. The relative intensities of
the fluorescence and phosphorescence of the copolymers can
be tuned by the initial feed ratio of two monomers or energy
transfer between two fluorescent and phosphorescent units. It
also provides an alternative and easy way to achieve dual
emissive oxygen sensing.
Synthesis of Platinum(II) 5,15-Bis(pentafluorophenyl)-10,20-
bis(4-bromophenyl)porphyrin.12c,d K2[PtCl4] (0.937 g, 2.26
mmol) and 5,15-bis(pentafluorophenyl)-10,20-bis(4-bromophenyl)-
porphyrin (0.717 g, 0.753 mmol) were added to a dry round-
bottomed 100 mL flask with 50 mL of anhydrous benzonitrile and
degassed with a stream of N2 for 10 min. The solution was stirred and
refluxed under N2 at 180 °C for 2 days, the mixture was cooled, and
the solvent was removed under vacuum. Column chromatography
(silica, 1/2 CH2Cl2/hexane v/v) afforded the Pt(II) porphyrin
complex as the first moving band. Removal of the solvent under
vacuum gave a solid that was recrystallized to give 0.620 g of Pt(II)
EXPERIMENTAL SECTION
■
Characterization Techniques for Materials. Mass spectra were
recorded with a high-resolution Finnigan MAT-95 mass spectrometer.
UV−vis absorption spectra were measured with a PerkinElmer UV/
vis/near-IR Lambda 900 spectrophotometer. All emissive measure-
ments were detected by a Fluorolog 3 spectrofluorometer. Emissive
lifetimes were measured with a HoribaJobin Yvon fluorescence lifetime
spectrophotometer. Thermal analyses were measured on a Perki-
nElmer DSC7 and a TGA7 thermal analyzer with heating rates of 10
and 15 °C/min, respectively. The number-average molecular weight
(Mn) and weight-average molecular weight (Mw) of the polymers were
characterized in THF by gel permeation chromatography at 35 °C
(polystyrene as standard). The n/m ratios of the polymers were
determined by 1H NMR (in CDCl3). Elemental analyses were
performed at the Institute of Chemistry of the Chinese Academy of
Sciences, Beijing, People's Republic of China. All 1H and 19F NMR (in
CDCl3) spectra were collected on Bruker 300 and 400 NMR
spectrometers, respectively. For oxygen sensing, standard gas mixtures
containing 0, 10, 21, 40, 60, 80, and 100% of O2 balanced with N2
(100, 90, 79, 60, 40, 20, and 0%, respectively) were passed through the
cuvette to equilibrate the oxygen content to the respective
concentrations and to monitor the changes of sensor luminescence.
Materials. The polymers PFO and PtP1−PtP3 were prepared by
the method shown in Figure 1.12
1
porphyrin complex as brown-red crystals (yield 72%). H NMR (300
MHz, CDCl3): δ (ppm) 8.90−8.70 (dd, 8 H), 8.01 (m, 4 H), 7.90 (m,
4 H). MS (FAB): calcd for C44H16N4F10Br2Pt 1145.51, found 1146.32.
Anal. Calcd: C, 46.14; H, 1.41; N, 4.89. Found: C, 46.31; H, 1.52; N,
4.90. UV−vis absorption: 395, 508, 541 nm (CH2Cl2); 399, 510, 541
nm (thin film). Photoluminescence (phosphorescence): 650, 713 nm
(CH2Cl2); 650, 710 nm (thin film).
Synthesis of Polymers PFO, PtP1, PtP2, and PtP3.12a,e,f
Ni(COD)2 (0.303 g, 1.10 mmol), 2,2′-dipyridyl (0.172 g, 1.10 mmol),
and 1,5-cyclooctadiene (0.119 g, 1.10 mmol) were added in a 25 mL
flask with 4.0 mL of toluene. After three freeze−thaw cycles, the
catalyst was heated to 80 °C for 1/2 h to form the purple complex. 2,7-
Dibromo-9,9-octylfluorene (0.261 g, 0.475 mol) and Pt(II) 5,15-
bis(pentafluorophenyl)-10,20-bis(4-bromophenyl)porphyrin complex
(0.0286 g, 0.025 mmol) were added to the solution and heated at
80 °C for another 4 days under N2. After it was cooled to room
temperature, the reaction mixture was poured into 100 mL of hexane.
The solid was filtered and then washed with dilute NH4OH, dilute
HCl, dilute NH4OH, acetone, and methanol in that order. The residue
was redissolved in chloroform and precipitated in a 100 mL mixture of
methanol and acetone (1/1, v/v). The yellow-brown solid was dried
under vacuum at 60 °C for 48 h to give 0.123 g of PtP1 (yellow-brown
solid) (yield 52%). The ratio of the monomers was varied for the
different copolymer compositions. Data for PtP1: 1H NMR (300
MHz, CDCl3) δ (ppm) 7.85 (d, 2H), 7.67 (m, 4H), 2.12 (m, 4H),
1.25−1.05 (m, 24H), 0.83 (t, 6H); 19F NMR (400 MHz, CDCl3) δ
(ppm) −136.5 (4F, dd, ortho), −151.4 (2F, t, para), −161.6 (4F, m,
meta). Data for PFO: 1H NMR (300 MHz, CDCl3) δ (ppm) 7.85 (d,
2H), 7.68 (m, 4H), 2.13 (m, 4H), 1.25−1.05 (m, 24H), 0.83 (t, 6H);
Synthesis of 5-(Pentafluorophenyl)dipyrromethane.12a Pyr-
role (50.0 mL, 720 mmol) and 2,3,4,5,6-pentafluorobenzaldehyde
(5.34 g, 27.2 mmol) were added to a dry round-bottomed 100 mL
flask and degassed with a stream of N2 for 10 min. Trifluoroacetic acid
(210 μL, 2.72 mmol) was then added, and the solution was stirred
under N2 at room temperature for 5 min and then quenched with 0.1
M NaOH (20 mL). A 100 mL portion of ethyl acetate was then added.
The organic phase was washed with 4 × 80 mL of water and dried
(Na2SO4), and the solvent was removed under vacuum to afford an
orange oil. Bulb-to-bulb distillation typically gave an oil which
crystallized upon standing (distilled at 150−160 °C (0.03 mmHg)).
The resulting oil was difficult to recrystallize directly; therefore, it was
dissolved by ethyl acetate. Removal of the solvent under vacuum gave
a solid that was recrystallized two times from ethanol/water (1/1, v/v)
to give 5.50 g of 5-(pentafluorophenyl)dipyrromethane as colorless
1
light yellow solid; yield 72%. Data for PtP2: H NMR (300 MHz,
CDCl3) δ (ppm) 9.05 (s, 0.37 H), 8.84 (d, 0.37 H), 8.29 (s, 0.37 H),
8.16 (s, 0.37 H) 7.86 (d, 2H), 7.68 (m, 4H), 2.14 (m, 4H), 1.25−1.05
(m, 24H), 0.83 (t, 6H); 19F NMR (400 MHz, CDCl3): δ (ppm)
−136.7 (4F, dd, ortho), −151.4 (2F, t, para), −161.6 (4F, m, meta);
1
red solid; yield 40%. Data for PtP3: H NMR (300 MHz, CDCl3) δ
(ppm) 9.05 (s, 1.0 H), 8.83 (d, 1.0 H), 8.30 (s, 1.0 H), 8.16 (s, 1.0 H)
7.85 (d, 2H), 7.68 (m, 4H), 2.13 (m, 4H), 1.25−1.05 (m, 24H), 0.83
(t, 6H); 19F NMR (400 MHz, CDCl3) δ (ppm) −136.7 (4F, dd,
ortho), −151.4 (2F, t, para), −161.5 (4F, m, meta); brown-red solid;
yield 28%.
1
crystals (yield 65%). H NMR (300 MHz, CDCl3): δ (ppm) 8.15 (br
s, 2 H), 6.74−6.73 (m, 2 H), 6.16 (q, 2 H), 6.02 (m, 2 H), 5.90 (s, 1
H), MS (EI): calcd for C15H9N2F5 312.24, found: 312.32. Anal. Calcd:
C, 57.70; H, 2.90; N, 8.97. Found: C, 57.69; H, 2.87; N, 9.01.
Synthesis of 5,15-Bis(pentafluorophenyl)-10,20-bis(4-
bromophenyl)porphyrin.12b 4-Bromobenzaldehyde (0.925 g, 5.00
mmol) and 5-(pentafluorophenyl)dipyrromethane (1.56 g, 5.00
mmol) were added to a dry round-bottomed 1 L flask with 500 mL
of CH2Cl2 and degassed with a stream of N2 for 10 min. BF3·O(Et)2
(0.418 mL, 1.65 mmol) was then added, the solution was stirred under
N2 at room temperature for 1 h, and then 2,3-dichloro-5,6-dicyano-1,4-
benzoquinone (DDQ; 860 mg, 3.80 mmol) was added. The mixture
Oxygen Quenching. In this approach, the O2 dependence on the
emission intensity is described by the Stern−Volmer expression, I0/I =
1 + KSV [O2], where I0 and I denote the emission intensities in the
absence of oxygen and at a oxygen concentration, [O2] is the oxygen
concentration or partial pressure in the solution, and KSV is the Stern−
Volmer quenching constant. [O2] can be calculated by [O2]=
SO [p(O2)], where the proportionality constant, SO , is the oxygen
2
2
solubility defined by Henry’s law (SO = 4.8 × 10−2 for the solution of
2
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1,2-dichloroethane at room temperature of 25 °C; http://www.epa.
gov/athens/learn2model/part-two/onsite/esthenry.html) and p(O2)
is the oxygen partial pressure above the solution.
G. Q.; Chen, J. B.; Payne, S. J.; Kooi, S. E.; Demas, J. N.; Fraser, C. L. J.
Am. Chem. Soc. 2007, 129, 8942−8943. (f) Zhang, G. Q.; Palmer, G.
M.; Dewhirst, M. W.; Fraser, C. S. Nat. Mater. 2009, 8, 747−751.
(g) Liu, Y. F.; Guo, H. M.; Zhao, J. Z. Chem. Commun. 2011, 47,
11471−11473. (h) Van Houten, K. A.; Heath, D. C.; Barringer, C. A.;
Rheingold, A. L.; Pilato, R. S. Inorg. Chem. 1998, 37, 4647−4653.
(i) He, Z.; Wong, W. Y.; Yu, X. M.; Kwok, H. S.; Lin, Z. Y. Inorg.
Chem. 2006, 45, 10922−10937.
(10) (a) Xiang, H. F.; Yu, S. C.; Che, C. M.; Lai, P. T. Appl. Phys.
Lett. 2003, 83, 1518−1520. (b) Che, C. M.; Hou, Y. J.; Chan, M. C.
W.; Guo, J. H.; Liu, Y.; Wang, Y. J. Mater. Chem. 2003, 13, 1362−1366.
(c) Xiang, H. F.; Li, C. N.; Yu, S. C.; Che, C. M.; Lai, P. T.; Chui, P. C.
Proc. SPIE 2004, 5519, 218−225.
(11) Yamamoto, T.; Fukushima, N.; Nakajima, H.; Maruyama, T.;
Yamaguchi, I. Macromolecules 2000, 33, 5988−5994.
(12) (a) Xia, C. J.; Advincula, R. C. Macromolecules 2001, 34, 5854−
5859. (b) Littler, B. J.; Miller, M. A.; Hung, C. H.; Wagner, R. W.;
O’Shea, D. F.; Boyle, P. D.; Lindsey, J. S. J. Org. Chem. 1999, 64,
1391−1396. (c) Kwong, R. C.; Sibley, S.; Dubovoy, T.; Baldo, M.;
Forrest, S. R.; Thompson, M. E. Chem. Mater. 1999, 11, 3709−3713.
(d) Tyulyaeva, E. Y.; Lomova, T. N.; Andrianova, L. G. Russ. J. Inorg.
Chem. 2001, 46, 371−375. (e) Yamamoto, T.; Morita, A.; Miyazaki, Y.;
Maruyama, T.; Wakayama, H.; Zhou, Z. H.; Nakamura, Y.; Kanbara,
T.; Sasaki, S.; Kubota, K. Macromolecules 1992, 25, 1214−1223.
(f) Xiang, H. F. Ph.D. Thesis; The University of Hong Kong, Hong
Kong, People's Republic of China, 2005.
ASSOCIATED CONTENT
■
S
* Supporting Information
1
Figures giving H NMR spectra of the polymers, absorption,
excitation and PL spectra of 5,15-bis(pentafluorophenyl)-10,20-
bis(4-bromophenyl)porphyrin and its Pt(II) complex in
CH2Cl2, and absorption and emission spectra of the thin
films of the polymers. This material is available free of charge
via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: xianghaifeng@scu.edu.cn (H.X.). Fax: (+86) 28-8541-
2291.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (No. 21172160) and Ministry of
Education of China (No. 20100181120039).
REFERENCES
■
(1) (a) Bernius, M. T.; Inbasekaran, M.; O’Brien, J.; Wu, W. S. Adv.
Mater. 2000, 12, 1737−1750. (b) Dimitrakopoulos, C. D.; Malenfant,
P. R. L. Adv. Mater. 2002, 14, 99−117. (c) McNeill, C. R.; Greenham,
N. C. Adv. Mater. 2009, 21, 3840−3850. (d) Wu, H. B.; Ying, L.; Yang,
W.; Cao, Y. Chem. Soc. Rev. 2009, 38, 3391−3400.
(2) (a) Leclerc, M. Adv. Mater. 1999, 11, 1491−1498. (b) Gerard,
M.; Chaubey, A.; Malhotra, B. D. Biosens. Bioelectron. 2002, 17, 345−
359. (c) Adhikari, B.; Majumdar, S. Prog. Polym. Sci. 2004, 29, 699−
766.
(3) Smela, E. Adv. Mater. 2003, 15, 481−494.
(4) (a) Wang, Q.; Yu, L. P. J. Am. Chem. Soc. 2000, 122, 11806−
11811. (b) Ng, P. K.; Gong, X.; Chan, S. H.; Lam, L. S. M.; Chan, W.
K. Chem. Eur. J. 2001, 7, 4358−4367. (c) Wong, W. Y.; Lu, G. L.;
Choi, K. H.; Shi, J. X. Macromolecules 2002, 35, 3506−3513. (d) Chan,
W. K.; Gong, X.; Ng, W. Y. Appl. Phys. Lett. 1997, 71, 2919−2921.
(e) Galbrecht, F.; Yang, X. H.; Nehls, B. S.; Neher, D.; Farrella, T.;
Scherf, U. Chem. Commun. 2005, 2378−2380. (f) Hou, Q.; Zhang, Y.;
Li, F. Y.; Peng, J. B.; Cao, Y. Organometallics 2005, 24, 4509−4518.
(5) (a) Mills, A. Platinum Met. Rev. 1997, 41, 115−127. (b) Amao, Y.
Microchim. Acta 2003, 143, 1−12. (c) Ramamoorthy, R.; Dutta, P. K.;
Akbar, S. A. J. Mater. Sci. 2003, 38, 4271−4282. (d) Khalil, G. E.;
Gouterman, M. P.; Green, E. US Patent 4,810,655, 1989. (e) Lee, S.
K.; Okura, I. Anal. Commun. 1997, 34, 185−188. (f) Obata, M.;
Matsuura, N.; Mitsuo, K.; Nagai, H.; Asai, K.; Harada, M.; Hirohara,
S.; Tanihara, M.; Yano, S. J. Polym. Sci., Part A 2010, 48, 663−670.
(6) Chu, B. W. K.; Yam, V. W. W. Langmuir 2006, 22, 7437−7437.
(7) Sanchez-Barragan, I.; Costa-Fernandez, J. M.; Valledor, M.;
Campo, J. C.; Sanz-Medel, A. Trends Anal. Chem. 2006, 25, 958−967.
(8) (a) Evans, R. C.; Douglas, P.; Williams, J. A. G.; Rochester, D. L.
J. Fluoresc. 2006, 16, 201−206. (b) Wang, X. D.; Chen, X.; Xie, Z. X.;
Wang, X. R. Angew. Chem. 2008, 120, 7560−7563. (c) Cywinski, P. J.;
Moro, A, J.; Stanca, S. E.; Biskup, C.; Mohr, G. J. Sens. Actuators B
2009, 135, 472−477. (d) Amelia, M.; Lavie-Cambot, A.;
McClenaghan, N. D.; Credi, A. Chem. Commun. 2011, 47, 325−327.
(9) (a) Kostov, Y.; Harms, P.; Pilato, R. S.; Rao, G. Analyst 2000,
125, 1175−1178. (b) Kostov, Y.; Rao, G. Sens. Actuators B 2003, 90,
139−142. (c) Hochreiner, H.; Sanchez-Barragan, I.; Costa-Fernandez,
J. M.; Sanz-Medel, A. Talanta 2005, 66, 611−618. (d) Valledor, M.;
Campo, J. C.; Sanchez-Barragan, I.; Viera, J. C.; Costa-Fernandez, J.
M.; Sanz-Medel, A. Sens. Actuators B 2006, 117, 266−273. (e) Zhang,
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