New bead type and high symmetrical diallyl-POSS based emissive conjugated polyfluorene

Article abstract of DOI:10.1016/j.polymer.2014.10.071

A new bead type and diallyl-POSS based polyfluorene (P2) with high symmetrical structure was synthesized via Heck coupling reaction between oligomeric alkynyl fluorene (P1) and diallyl polyhedral oligomeric silsesquioxanes (diallyl-POSS). The molecular we

Full text of DOI:10.1016/j.polymer.2014.10.071

Accepted Manuscript
New Bead Type and High Symmetrical Diallyl-POSS Based Emissive Conjugated
Polyfluorene
Jin Huang, Weina Wang, Jiangjing Gu, Weizhi Li, Qiuhong Zhang, Yin Ding, Kai Xi,
Youxuan Zheng, Xudong Jia
PII:
S0032-3861(14)01004-0
10.1016/j.polymer.2014.10.071
JPOL 17388
DOI:
Reference:
To appear in: Polymer
Received Date: 6 July 2014
Revised Date: 13 October 2014
Accepted Date: 30 October 2014
Please cite this article as: Huang J, Wang W, Gu J, Li W, Zhang Q, Ding Y, Xi K, Zheng Y, Jia X, New
Bead Type and High Symmetrical Diallyl-POSS Based Emissive Conjugated Polyfluorene, Polymer
(2014), doi: 10.1016/j.polymer.2014.10.071.
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ACCEPTED MANUSCRIPT
New Bead Type and High Symmetrical Diallyl-POSS Based
Emissive Conjugated Polyfluorene
a,b
a,b
a,b
a,b
a,b
c
b
Jin Huang, Weina Wang, Jiangjing Gu, Weizhi Li, Qiuhong Zhang, Yin Ding, Kai Xi,
a
*,a,b
Youxuan Zheng, Xudong Jia
a
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, Nanjing
University, Nanjing 210093, PR China
b
Department of Polymer Science & Engineering, Nanjing University, Nanjing 210093, PR China
c
State Key Laboratory of Analytical Chemistry for Life Science, Nanjing University, Nanjing 210093, PR China
ABSTRACT: A new bead type and diallyl-POSS based polyfluorene (P2) with high symmetrical
structure was synthesized via Heck coupling reaction between oligomeric alkynyl fluorene (P1)
and diallyl polyhedral oligomeric silsesquioxanes (diallyl-POSS). The molecular weight and the
conjugated length of P1 and P2 were well controlled to acquire good solubility and excellent
optical property. The bead-type POSS based polymer was characterized by gel permeation
1
chromatography (GPC), FT-IR, H NMR and photoluminescence (PL) spectra. High Resolution
Transmission Electron Microscopy (HRTEM) micrographs showed that diallyl-POSS were
uniformly nano-dispersed in the polymer matrix. Compared with P1, the POSS-based
polyfluorene P2 exhibited not only a higher thermal stability, but also an improved photophysical
property in solution and solid states. The incorporation of diallyl-POSS resulted effectively in
inhibiting the strong stacking/dipole–dipole interaction between fluorescent groups in the
polyfluorene. The experimental results indicate that the bi-functional POSS based light-emitting
polymers with high symmetrical structure can have great potential in optical materials and devices,
such as OPV or PLED, etc.
Keywords: Diallyl-POSS, polyfluorene, light-emitting polymer.
1
. Introduction
_
_____________________
*
Corresponding authors. Tel: +86-25-83593041; Fax: +86-25-83621337.
E-mail addresses: jiaxd@nju.edu.cn (X. D. Jia).

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Semiconductor light-emitting polymers have attracted extensive attention on account of their great
application prospect in the fields of organic photovoltage (OPV) [1], polymer light-emitting diode
(PLED) [2], biological imaging [3], photodynamic therapy [4], sensing [5], etc. In recent years,
semiconductor light-emitting polymers containing polyfluorene structure have been a hotspot
because of their high fluorescence efficiency [6], excellent two-photon fluorescence property [7],
remarkable chemical/thermal stability [8], and extraordinary electronic transmission property [9].
However, serious fluorescence quenching exists, which is attributed to a strong dipole–dipole and
π–π stacking interaction between the chromophores [10]. Furthermore, the emission spectra of
polyfluorene materials always exhibit shoulder peaks around 530 nm, which affects the emission
color purity. In view of this, the application of polyfluorene in luminescent material has been
hindered [11].
To break these bottle-necks, one approach is to introduce POSS into polyfluorene optical
materials [12]. It is known that the incorporation of a particular cage structure consisting of
inorganic Si-O core can improve the thermal stability and photo-stability [13]. Additionally, the
appropriate numbers of external organic groups of POSS with good symmetry could avoid
functional groups lying in closer proximity to each other, which would reduce the opportunity for
self-absorption thus enhance fluorescence quantum yield [14]. So far, copious cross-linked
structures [15], pendt-type [16], star-type [17] POSS-based polyfluorene polymers have been
synthesized to overcome the formation of aggregation or keto defect in polyfluorenes.
Recently, Laine et al. have studied the photophysical properties of T (octahedral POSS), T10
8
(
decahedral POSS) and T (dodecahedral POSS) with p-vinylstilbene structure and found that the
12
size of Si-O cage and the symmetry of the structure can significantly impact on fluorescence
quantum yield [18]. More importantly, the incorporation of POSS with symmetrical structure
greatly enhances the two-photon fluorescence (TPF) and two-photon absorption (TPA) cross
section on account of very rigid Si-O cage.

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Scheme 1. Construction of diallyl-POSS bridged organic-inorganic luminescent polyfluorene.
However, few researches have been reported about bead-type POSS-based light-emitting
polymers. In this article, diallyl-POSS (T D type) with highly symmetrical structure was
8
2
synthesized, and a diallyl-POSS-based hybrid polymer with bead type structure was then prepared
Scheme 1). Meanwhile, the conjugation length of oligomeric alkynyl fluorene structure between
(
the adjacent diallyl-POSS, which was nailed on the main chain of polymer via Heck
cross-coupling reactions, was well controlled in order to acquire excellent luminescent properties
and solubility. The incorporation of “huge” inorganic POSS nanoparticles to form bead type and
high symmetrical diallyl-POSS based polymer molecular chain was expected to improve not only
the thermal property of light-emitting polymer, but also the optical properties including a higher
fluorescent quantum yield, enhanced photo-stability and much improved two-photon fluorescence
(TPF) property. It is expected that bifunctional-POSS based polymer will have great impact on
applications in optical materials and devices, such as OPV or PLED, etc.
2
. Experimental Section
2
.1. Materials
1
-Bromodecane (98%), 2,7-dibromofluorene (98%), tetrabutyl ammoniumbromide (98%),
carbazole (98%), bis(triphenylphosphine) palladium (II) chloride (98%) purchased from Nanjing
Carbon Reagent Co. Ltd. Cuprous iodide (99%), 2-methylbut-3-yn-2-ol (98%),
1
,10-dibromodecane (98%), sodium hydroxide and anhydrous potassium carbonate (98%) were
used as received from Adamas. Allyl(dichloro)methylsilane (95%) was obtained from TCI

ACCEPTED MANUSCRIPT
(Shanghai) Chemical Industry Development Co., Ltd. Tetrasilanolphenyl POSS was purchased
from Hybrid Plastics. All organic solvents were purchased from commercial sources and were
carefully dried and distilled prior to use.
2
2
.2. The synthesis of monomers and polymers
.2.1. 2,7-dibromo-9,9-didecylfluorene (1). 1-Bromodecane (4.42 g, 20.0 mmol) was added by
syringe to a mixture of 2,7-dibromofluorene (2.59 g, 8 mmol), tetrabutyl ammonium bromide
0.02 g, 0.064 mmol) and 2.50 mL of 50% aqueous sodium hydroxide in dimethyl sulfoxide (50.0
(
mL). After stirring at room temperature for 4 h, the mixture was poured into water and extracted
three times with dichloromethane. The solvent was removed under reduced pressure and the
precipitate was purified by column chromatography on silica gel (eluent: petroleum ether) to
1
afford 2,7-dibromo-9,9-didecylfluorene as a white powder (4.45 g, Yield 92%). H NMR (500
MHz, CDCl , δ): 7.51 (d, 2H, J = 8.70 Hz, Ar–H), 7.45 (m, 4H, Ar–H), 1.91 (m, 4H, CH ), 1.13
3
2
-
1
(
m, 28H, CH ), 0.85 (t, 6H, J = 6.95 Hz, CH ), 0.58 (m, 4H, CH ). FT-IR (cm , KBr): ν = 2950,
2 3 2
2
7
2
836 (s; CH), 1638, 1551 (w; Ar). Anal. Calcd. for C H Br : C 65.56, H 8.00; Found: C 64.72, H
33 48 2
.62.
.2.2. 4,4’-(9,9-didecyl-9H-fluorene-2,7-diyl)bis(2-methylbut-3-yn-2-ol) (2). Under argon
atmosphere, 2,7-dibromo-9,9-didecylfluorene (1.21 g, 2 mmol), 2-methylbut-3-yn-2-ol (1.6 mL,
6 mmol), bis(triphenylphosphine) palladium(II) chloride (24 mg, 0.08 mmol) and cuprous iodide
8 mg, 0.04 mmol) were dissolved in 20 mL of triethylamine and 40 mL of tetrahydrofuran. The
1
(
mixture was refluxed at 70 °C for 24 h. After cooling to room temperature, the insoluble substance
was filtered off. Then the solvent was removed under reduced pressure. The mixture was extracted
three times with dichloromethane. The organic phase was purified by column chromatography on
silica
gel
with
ethyl
acetate/petroleum
ether
(1:8
v/v)
to
afford
4
,4’-(9,9-didecyl-9H-fluorene-2,7-diyl)bis(2-methylbut-3-yn-2-ol) as a yellow powder (0.87 g,
1
Yield 71%). H NMR (500 MHz, CDCl , δ): 7.59 (d, J = 7.9 Hz, 2 H, Ar–H), 7.39 (m, 4 H, Ar–H),
3
1
.92 (m, 4H, CH ), 1.66 (s, 12H, CH ), 1.28–1.02 (m, 28H, CH ), 0.85 (t, J = 7.15 Hz, 6 H)ꢀ0.54
2 3 2
-1
(
m, 4H, CH ). FT-IR (cm , KBr): 3330 (m; OH), 2927, 2856 (s; CH), 2220 (w; C≡C), 1622, 1541
2
(
w; Ar). Anal. Calcd. For C H O : C, 84.39; H, 10.20. Found: C, 84.53; H, 10.23.
4
3
62
2
2
.2.3.
9,9-didecyl-2,7-diethynylfluorene
(3).
Under
argon
atmosphere,

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4
,4’-(9,9-didecyl-9H-fluorene-2,7-diyl)bis(2-methylbut-3-yn-2-ol) (0.61 g, 1 mmol) and sodium
hydroxide (0.60 g, 10 mmol) in 40 mL of 1,4-dioxane were refluxed at 80 °C for 6 h. After cooling
to room temperature, water and dichloromethane were added to the mixture, and the organic phase
purified by column chromatography on silica gel with petroleum to get
1
9
,9-didecyl-2,7-diethynylfluorene as white crystals (0.46 g, Yield 92%). H NMR (500 MHz,
CDCl , δ): 7.62 (d, J = 8.0 Hz, 2 H, Ar–H), 7.46 (m, 4 H, Ar–H), 3.13 (s, 2 H, CꢁC–H), 1.93 (m,
3
1
3
4
H, CH ), 1.25–1.02 (m, 28H, CH ), 0.85 (t, J = 7.2 Hz, 6 H, CH ), 0.56 (m, 4H, CH ). C NMR
2 2 3 2
(
500 MHz, CDCl , δ): 151.04, 141.02, 131.35, 126.56, 121.07, 119.94, 84.54, 77.47, 55.27, 40.30,
3
-1
3
1.98, 30.03, 29.83, 29.63, 29.35, 29.31, 23.73, 22.72, 14.19. FT-IR (cm , KBr): 3310 (s; CꢁC–
H), 2924, 2850 (s; CH), 2100 (w; CꢁC), 1638, 1573 (m; Ar). Anal. Calcd. For C H : C, 89.81;
3
7
50
H, 10.19. Found: C, 89.67; H, 10.23.
.2.4. 9-(10-bromodecyl)-9H-carbazole (4). Under argon atmosphere, carbazole (1.67 g, 0.01 mol),
anhydrous potassium carbonate (2.77 g, 0.02 mol), and 1,10-dibromodecane (6.00 g, 0.02 mol) in
0 mL of anhydrous acetonitrile were refluxed at 95 °C for 36 h. After cooling to room
2
4
temperature, insoluble substance was filtered, and the solvent was removed under reduced
pressure. The crude product was purified by column chromatography on silica gel with petroleum
1
to get 9-(10-bromodecyl)-9H-carbazole as white crystals (1.66 g, Yield 43%). H NMR (500 MHz,
CDCl , δ): 8.08 (d, J = 7.7 Hz, 2 H, Ar–H), 7.43 (t, J = 7.8 Hz, 2 H, Ar–H), 7.35 (d, J = 8.1 Hz, 2
3
H, Ar–H), 7.20 (t, J = 7.5 Hz, 2 H, Ar–H), 4.21 (t, J = 7.3 Hz, 2 H, CH ), 3.33 (t, J = 6.8 Hz, 2 H,
2
-1
CH Br), 1.79 (m, 4 H, CH ) , 1.33–0.91 (m, 12 H, CH ). FT-IR (cm , KBr): 2930, 2850 (s; CH),
2
2
2
1
6
2
9
2
0
632, 1619, 1593 (m; Ar). Anal. Calcd. For C H BrN: C, 68.39; H, 7.30; N, 3.63; Found: C,
22 28
8.47; H, 7.25; N, 3.56.
.2.5. 9,9’-((2,7-dibromo-9H-fluorene-9,9-diyl)bis(decane-10,1-diyl))bis(9H-carbazole)
(5).
-(10-bromodecyl)-9H-carbazole (1.55 g, 4 mmol) was added by syringe to a mixture of
,7-dibromofluorene (0.32 g, 1 mmol), tetrabutyl ammonium bromide (3 mg, 0.008 mmol) and
.313 mL of 50% aqueous sodium hydroxide dissolved in dimethyl sulfoxide (10.0 mL). After
stirring at 40°C for 6 h, the mixture was poured into water and extracted three times with
dichloromethane. The solvent was removed under reduced pressure. The precipitate was purified
by column chromatography on silica gel ethyl acetate/petroleum (1:20 v/v) to afford
9
,9’-((2,7-dibromo-9H-fluorene-9,9-diyl)bis(decane-10,1-diyl))bis(9H-carbazole)
as
white

ACCEPTED MANUSCRIPT
1
crystals (0.36 g, Yield 38%). H NMR (500 MHz, CDCl , δ): 8.08 (d, J = 7.5 Hz, 4 H, Ar–H), 7.46
3
(
m, 14 H, Ar–H), 7.21 (d, J = 7.4 Hz, 4 H, Ar–H), 4.25 (t, J = 7.6 Hz, 4 H, CH ), 1.89–1.78 (m, 8
2
1
3
H, CH ), 1.31–0.95 (m, 24 H, CH ), 0.53 (m, 4 H, CH ). C NMR (500 MHz, CDCl , δ): 152.56,
2
2
2
3
1
40.45, 139.11, 130.21, 126.19, 125.61, 122.86, 121.52, 121.20, 120.38, 118.72, 108.69, 55.73,
-1
4
3.09, 40.16, 29.79, 29.41, 29.38, 29.36, 29.10, 28.97, 27.32, 23.62. FT-IR (cm , KBr): 2936,
2
861 (s; CH), 1636, 1621, 1582 (m; Ar). Anal. Calcd. For C H Br N : C, 73.23; H, 6.68; N, 3.00;
5
7
62
2
2
Found: C, 73.34; H, 6.82; N, 2.93.
2
.2.6. 3,13-di(3-propenyl)-3,13-dimethyl-1,5,7,9,11,15,17,19-octaphenylhexacyclo [15.3.1(1,13).
(3,11).1(5,17).1(9,15)]decasiloxane (6). 6 was synthesized according to the pathway shown in
1
Scheme 2:
Scheme
2.
Synthesis
of
3,13-di(3-propenyl)-3,13-dimethyl-1,5,7,9,11,15,17,19-octaphenylhexacyclo
[15.3.1(1,13).1(3,11).1(5,17).1(9,15)]decasiloxane.
Under dry argon atmosphere, allyl(dichloro)methylsilane (3.102 g, 1.46 mL, 10 mmol) was
added dropwise to a mixed solution of 40 mL of anhydrous tetrahydrofuran, tetrasilanolphenyl
POSS (5.350 g, 5 mmol), and triethylamine (0.81 ml, 5 mmol) at room temperature. After 30
minutes, the insoluble solid was filtered off and the solvent and other volatile compounds were
removed under reduced pressure. The crude product was washed with 50 mL of methanol, 5 mL of
ether and 2 mL of hydrochloric acid (1 mol/L) to afford cis- and trans-6 as a white powder (3.89 g,
1
Yield 63%). Cis- and trans-6 (in the presence of isomeric mixture of 1:1 ratio): H NMR (500
MHz, CDCl , δ): 7.53–7.19 (m, 40 H, Ar–H), 5.76 (m, 2 H, CH=CH ), 4.88–4.76 (m, 4 H,
3
2
2
9
CH=CH ), 1.77 (d, 4 H, J = 7.8 Hz, CH ), 0.30 (s, 6 H, CH , indicated isomeric mixture). Si
2
2
3
NMR (500 MHz, CDCl , δ): -21.96, -78.58, -79.49 (trans-6; relative intensity ratio 1:2:2); -21.96,
3
-1
-
78.58, -79.45, -79.53 (cis-6; relative intensity ratio 1:2:1:1). FT-IR (cm , KBr): 1639, 1591 (w;
Ar), 1097 (s; Si–O–Si). Anal. Calcd. For C H O Si : C, 54.51; H, 4.57; Found: C, 54.64; H,
5
6
56 14 10
+
4
.73. MALDI-TOF MS [C H O Si + Na] : Calcd. 1256.89, found 1255.25.
56 56 14 10

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2
.2.7. Synthesis of oligomeric alkynyl fluorene (P1). 9,9’-((2,7-dibromo-9H-fluorene-9,9-diyl)bis
(decane-10,1-diyl))bis(9H-carbazole) (701 mg, 0.75 mmol), 9,9-didecyl-2,7-diethynylfluorene
(247 mg, 0.5 mmol), tetrakis(triphenylphosphine) palladium(0) (23 mg, 2 mol %), copper iodide
(10 mg, 5 mol %), N,N-diisopropylamine (5 mL), and toluene (10 mL) were added into a Schlenk
flask in a nitrogen-filled glove box. After stirring at 60 °C for 12 h, the dibromo monomer (5) (94
mg, 0.10 mmol) in THF (5 mL) was added from a syringe. After another 12 hours at 60 °C, the
polymer was precipitated into methanol, and the solid was filtered and washed in a Soxhlet
extractor with methanol followed by acetone to remove residual catalyst and
low-molecular-weight material. The crude product was purified by column chromatography on
silica gel tetrahydrofuran/hexane (3:1 v/v) to remove high molecular weight material. The yield
3
3
was 32% as an orange solid. Mw = 8.79×10 Da, M = 4.61×10 Da, PDI = 1.91, (GPC,
n
-1
1
polystyrene); FT-IR (cm , KBr): 2923, 2852 (CH), 1627, 1604, (Ar); H NMR (500 MHz, CDCl ,
3
δ): 8.07 (4H, Ar–H), 7.67–7.38 (20H, Ar–H), 7.21 (4H, Ar–H), 4.26 (4H, N–CH ), 1.87–0.54
2
(
78H, (CH ) and (CH ) CH ).
2 10 2 10 3
2
.2.8. Synthesis of bead-type POSS-based hybrid (P2). Bead-type POSS-based hybrid (P2) was
prepared from oligomeric alkynyl fluorine (P1) and diallyl-POSS (molar feed ratio 1:1) through
conventional Heck coupling reaction using palladium acetate as a catalyst, anhydrous potassium
o
carbonate as an acid binding agent, and N,N-dimethyl glycine (DMG) as a ligand at 120 C in dry
N-methyl pyrrolidone. Under dry argon atmosphere, a mixture of P1 (440 mg, 0.05 mmol),
diallyl-POSS (62 mg, 0.05 mmol), DMG (31 mg, 0.3 mmol), palladium acetate (4 mg, 0.015
mmol), anhydrous potassium carbonate (21 mg, 0.015 mmol) and N-methyl pyrrolidone (5 ml)
were added into a Schlenk flask in a nitrogen-filled glove box and stirred at 120 °C for 20 h. After
cooling to room temperature, solvent was removed by vacuum distillation. The polymer was then
precipitated into water and filtered, washed in a Soxhlet extractor with acetone/dichloromethane
(6:1 v/v). The crude product was purified by column chromatography on silica gel tetrahydrofuran.
In this way, the much high molecular weight product could be removed to improve the solubility
4
4
of P2. The yield was 35% as a dark green solid. M = 3.93×10 Da, M = 1.45×10 Da, PDI =
w
n
1
2
.71, (GPC, polystyrene); H NMR (500 MHz, CDCl , δ): 8.09 (br, Ar–H), 7.67–7.36 (br, Ar–H),
3
7
.20 (br, Ar–H), 5.45 (br, CH=CH), 4.26 (br, N–CH ), 1.97–0.60 (br, (CH ) and (CH ) CH ).
2
2 10
2 10
3
2
9
-1
Si NMR (79.49 MHz, solid, δ): -18.12, -65.22, -79.10. FT-IR (cm , KBr): 2923, 2852 (CH),

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1
681, 1663, 1581 (Ar), 1118 (Si–O–Si).
2
.3. Preparation Fluorescent Composite Film
.89 g (0.04 mol) of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 20 g
0.02 mol) of poly-caprolactone diol (PCL M =1000) and 50 uL of dibutyltin dilaurate were added
8
(
w
to a three-necked bottle with mechanical agitation, and reacted 6 h at 80 °C. 1.80 g (0.02 mol) of
,4-butylene glycol (BDO) and 30 ml of THF were added after cooling to room temperature. The
1
mixture was used as matrix solution. 6 mg/ml THF solutions of P1 and P2 were prepared
respectively, and different volumes of P1 and P2 THF solution, according to different mass
fractions of P1 and P2 in fluorescence composite films, were added to 2 ml of the former matrix
solution with magnetic stirring. The mixture was then added to the teflon plate. The solvent was
evaporated 24 h at room temperature, and then was placed into an oven at 60 °C for 2 days.
Finally, the residue solvent was evaporated under vacuum at 30 °C for 10 h.
2
2
.4. Measurements and Techniques
.4.1. Molecular Structure Characterizations
Infrared spectra were obtained with a Bruker VECTOR 22 Fourier-transform infrared (FT-IR)
1
13
29
spectrometer. The H NMR, C HNR and Si NMR spectra were recorded in trichloromethane-d
2
9
using tetramethylsilane as internal standard on a Bruker 500 (500 MHz). The solid Si NMR
spectrum of P2 was obtained with Bruker AVANCE III (400MHz).
Elemental Analysis data were obtained using a CHN-O-Rapid elemental analyzer (Foss.
Heraeus, Germany). Matrix-assisted ultraviolet laser desorption/ionization time of flight mass
spectroscopy (MALDI-TOF-MS) of diallyl-POSS monomer was performed using a Bruker
Daltonics Autoflex TOF/TOF in linear and reflection modes. Gentisic acid (2,5-dihydroxybenzoic
acid, DHB) was used as the matrix with tetrahydrofuran as the solvent. Sodium was used as the
cationizing agent.
Molecular weight of polymers was measured on gel permeation chromatography (GPC)
apparatus equipped with UV-vis detection and Waters 1515 HPLC pump. Tetrahydrofuran was
used as a carrier solvent at a flow rate of 1.0 mL/min at 25 °C. A calibration curve was made to
6
determine M and M /M values with polystyrene standards, M ꢂ900ꢃ1.74×10 g/molꢀDꢄ
n
w
n
w

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1
.1. Simultaneous TG-DTA Netzsch STA 449F3 was used to investigate the thermal stability of
the polymers in nitrogen atmosphere from ambient temperature to 700 °C at a heating rate of
-1
1
0 °C min .
2
.4.2. Morphological Characterizations
Morphological observations were done by High Resolution Transmission Electron Microscopy
(HRTEM). The polymers were embedded by epoxy resin, and ultrathin sections were made by
using LeicaULTRACUT UC6 with approximate thickness about 70 nm. The ultrathin sections
were then collected onto copper grids. The copper grids were imaged using a JEM-2100
transmission electron microscope at 200 kV.
Surface topography was characterized by atomic force microscopy (AFM) in tapping mode
using silicon tips with Olympus OMCL-AC160TS and controller from Veeco Corporation. The
sample was spin-coated on silicon wafer surface by THF solutions of P2 films (2 wt ‰) and cured
in a vacuum oven at 334 K for 12 h.
2
.4.3. Optical Performance Characterizations
Ultraviolet-visible (UV-vis) absorption of the obtained polymers solution was carried on a
UV-1800 (PC) UV-vis spectrophotometer (Mapada, China). The solution fluorescence spectrums
of the compound were measured with a FluoroMax-4 spectrofluorometer (HORIBA Scientific,
Japan). The solid thin films of polymers were prepared by spinning coating 10 mg/ml polymer
solution on the quartz glass plate with a spin rate of 2000 rpm. The solid thin film of polymers and
the fluorescent composite films fluorescence spectrums were recorded on a FP-6600 (Jasco Inc.)
spectrophotometer using a quartz cell with an optical path length of 1 mm. The
photoluminescence QYs were determined on the spectrophotometer with an integrating sphere
(
ISF-513). TPF spectra of P1 and P2 in dilute solution and TPF imaging of composite films were
performed using Leica TCS SP5 laser scanning confocal microscope with a Ti:sapphire laser
Mira Optima 900F, Coherent) as the excitation source. The laser is tuned at 780 nm with 0.5 mW
(
power after the objective and provides ca. 100-fs pulses at a repetition rate of 76 MHz. The details
of the two-photon technique experimental setup are described elsewhere [19].
3
. Results and Discussion

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3
.1. Synthesis and Characterization
An appropriate conjugation length and molecular weight are crucial factors to influence the
property of solubility and emission for the light-emitting polymer. In this work, the molecular
weight and the conjugated length of P1 were controlled by adding excess amount of monomers 5
step by step in the synthesis procedure, followed by washing repeatedly with acetone to remove
small molecules in the purification procedure and using column chromatography to take away
high molecular weight polymers to prevent insoluble substance generating in the next step
reaction (see Experimental Section). P1 was first synthesized through the Sonogashira coupling
reaction based on dibromo monomer 5 and double alkynyl monomer 3 with a molar ratio of 1.7:1.
At beginning of the reaction, dibromo monomer and alkynyl monomer were added according to
1
.5 eq. to 1 eq.. After 12 hours, another 0.2 eq. of dibromo monomer was added into the mixture to
ensure P1 was bromo-terminated polymer (Scheme 2) according to the reported end-capped
control method [20]. The linear polymer (P2) was then prepared from (P1) and diallyl-POSS
(molar ratio 1:1) through classic Heck coupling reaction. The conjugated length of P2 was entirely
depended on oligomeric alkynyl fluorene moiety from P1, and the molecular weight of P2 was
also controlled by column chromatography (see Experimental Section 2.2.8.).
Scheme 3. Synthesis of diallyl-POSS bridged linear polymer.

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The molecular weight and distribution of polymers were investigated by GPC. Fig. 1 shows the
retention time versus UV absorbance curves of P1 and P2. The molecular weight of P1 is M =
w
3
3
4
4
8
.79×10 Da and M = 4.61×10 Da, while P2 is M = 3.93×10 Da and M = 1.45×10 Da. The
n w n
GPC data indicated the linear polycondensation reaction between P1 and diallyl-POSS has
happened.

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Fig. 1. GPC profiles of P1 and P2.
The polycondensation reaction and the structures of P1, P2 and diallyl-POSS were confirmed
1
29
by the H NMR (Fig. 2), solid Si NMR, MALDI-TOF-MS and FT-IR spectra (see supplementary
material). The proton peaks of P1 at aromatic ring area are amplified and shown at δ ≈ 8.09 and
7
.67–7.36 ppm, respectively. While the broadening phenomenon of proton peak for P2 could be
observed at aromatic ring area, which are corresponded to the larger molecular weight of P2. The
characteristic peak at 4.26 ppm belongs to the proton of methylene linking to carbazolyl for P1
and P2. On the one hand, the characteristic peaks at δ ≈ 5.76 and 4.88–4.76 ppm are corresponded
to olefin proton of diallyl-POSS. For P2, the characteristic peak of olefin proton of diallyl-POSS
moiety turns into a doublet and broad peak at 5.45 ppm with the integral area ratio of 1:1, which
also confirms that P2 has been synthesized and the Heck coupling reaction was successful. In the
2
9
Si NMR spectrum of P2 (see supplementary material), P2 displayed three broad characteristic
signals at δ ≈ -18.12, -65.22, and -79.10 ppm, respectively. The signal at -18.12 ppm is assignable
to the silicon nucleus of Si(CH CH=CH)CH bond, and the signal at -65.22 ppm and -79.10 ppm
2
3
belong to the other two kinds of the silicon nucleus of Si–O–Si cage. Furthermore, the FT-IR
−
1
spectrum of P2 shows an intense characteristic Si–O–Si stretching vibration at 1118 cm for
diallyl-POSS (see supplementary material). The characteristic signals at 3055, 2923, 2852, 1681,

ACCEPTED MANUSCRIPT
-1
1
663, and 1581 cm respectively are corresponded to the oligomeric alkynyl fluorene moiety.
1
Fig. 2. The H NMR spectra of P1, P2 and diallyl-POSS.
3
.2. Thermal Stability
The thermal stability of the polymers was measured via the thermogravimetric analysis (TGA)
to study the influence of the introduction of diallyl-POSS. From TGA curves of P1 and P2 under
nitrogen (Fig. 3), it was observed that the thermal decomposition temperature (T , 5% weight
d
loss temperature) were 321 °C (P1) and 382 °C (P2), respectively. In other words, the T value of
d
P2 was 61 °C higher than that of P1. It indicates that the incorporation of diallyl-POSS can
effectively enhance the thermal stability of the luminescent material due to the presence of
inorganic Si–O cage shielding effect, which limits the heat transfer and protects the organic part
of polymer from the heat effect of attack [21].

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Fig. 3. TGA thermograms of P1, P2, at a ramp rate of 10 °C/min in nitrogen flow.
3
.3. The morphologies of P1 and P2 films
HRTEM was used to analyze the microstructure of P2 and P1. The diallyl-POSS connected to
polyfluorene could be seen from the ultrathin sections of polymer embedded in epoxy resin. There
are only a small quantity of 5–10 nm nanoparticles in P2 sample [Fig. 4(a)], corresponding to
diallyl-POSS aggregates. The same phenomenon can be seen in our previous work [22]. While a
certain amount of smaller nanoparticles with the size of 2–3 nm are shown in the polymer matrix
[
Fig. 4(b) and 4(c)], which are uniformly nano-dispersed. It reveals that aggregation of the
inorganic POSS could be reduced, in that diallyl-POSS is fixed on the main chain of polyfluorene
via chemical bond and the bead-type POSS-based polymer has the symmetric structure. It could
also benefit for attenuate the strong dipole-dipole and π-π stacking interactions between
chromophores, which would acquire better properties for emissive conjunction polymers. This
result has been further confirmed with AFM images (Fig. S1), in which the aggregation of
diallyl-POSS multi-molecules are absent on the micron scale.

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Fig. 4. HRTEM micrographs for P2 (a, scale bar = 50 nm; b, scale bar = 10 nm; c, scale bar = 5 nm) and P1 (d,
scale bar = 50 nm; e, scale bar = 10 nm; f, scale bar = 5 nm).
3
.4. Optical Properties
3
.4.1. One-Photon Fluorescent Emission and Enhancement Fluorescent Quantum Yield (QY)
To study the impact of the incorporation of diallyl-POSS on the fluorescence emission of the
fluorescent polymers, the one-photon fluorescence spectra of P1 and P2 both in solution and solid
thin film state were acquired. The solid thin films of P1 and P2 were prepared by spin coating
method on the quartz plate, and then, the PL spectra of P1 and P2 in thin solid film were measured
(
Fig. 5). The maximum emission peaks of P1 and P2 at 428 nm are similar in THF solutions,
located at blue emission region. While in solid state, the aggregation effect leads to red shift of the
main peaks to 538 nm (P1) and 475 nm (P2), respectively. Compared with P1, P2 shows a larger
blue-shift, which is attributed to the reduction of the molecular-stacking-led aggregations by the
incorporation of large and rigid Si–O–Si cage [12b].

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Fig. 5. The emission spectra of P1 and P2 in THF solutions and thin films.
Simultaneously, the QY of P2 in dilute solution was calculated as 77.6% via reference method
23], which is higher than P1 of 71.3% (Table S1). The QYs of P1 and P2 in solid state were also
[
measured by a calibrated integrating sphere (ISF-513). The QY rises from P1 of 3.1% to P2 of
.7%. The experimental results suggest that the oligomeric alkynyl fluorene moiety, when was
5
nailed on the both ends of diallyl-POSS with highly symmetrical structure, can prevent the
chromophoric groups close to each other, resulting the decreased emission quenching and the
increased fluorescence quantum efficiency.
3
.4.2. Two-photon Fluorescence Enhancement
To explore the two-photon fluorescence (TPF) enhancement effect of the incorporation of
diallyl-POSS with symmetrical structure, the THF solutions of P1 and P2 with the same
-6
concentration (8.0×10 mol/L) of fluorescent groups (carbazole-fluorenyl and alkynyl-fluorenyl
copolymer unit) were prepared, and the two-photon fluorescence spectra are shown in Fig. 6.
Compared with P1, P2 afforded the greater TPF enhancement. At the same time, taking emission
peak at 428 nm as reference, the relative intensity of emission peak at 454 nm of P2 was
obviously weaker than that of P1. It reveals that, for P2, less excimers are formed in the solution

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and the aggregation effect attenuates. The remarkable TPF enhancement could also be attributed to
the abatement of aggregation effect between fluorescent groups when diallyl-POSS is coupled into
polymer molecular chain.
Fig. 6. The two-photon fluorescence spectra of P1 and P2 in THF solution with the same concentration of
-
6
fluorescent groups (8.0×10 mol/L).
3
.4.3. Photo-fading Experiment
Photo-stability is another crucial property for luminescent material, so photo-fading experiment
of P1 and P2 (Fig. 7) is performed to probe the influence of incorporation of diallyl-POSS into the
main chain of the light-emitting polymer. The THF dilute solutions of the polymers in 50 ml
volumetric flasks were placed 25 cm from a 1000 W iodine-tungsten lamp. A cold trap (10 L
solution of 50 g/L NaNO and 20 cm in length) was set up between the sample and the lamp. The
2
absorption spectra were recorded every 6 hours until 24 hours.

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Fig. 7. The photo-degradation rate curves of P1 and P2; Insert figures: The change of UV spectra under irradiation
o
from a 1000 W iodine–tungsten lamp of a) P1, b) P2 in THF at 25 C.
From the inserted figure, the attenuation degree of the maximum absorption peak value of P1
was obviously greater than that of P2 over time. Under low concentration, photo-degradation
equation can be simplified as ln (A /A ) = kt [24], in which “A ” represents the initial absorption
0
t
0
of λmax, “A ” means the absorption of λ during irradiation, and “k” is the photo-degradation
t
max
reaction rate constant. Accordingly, “k” value could be acquired from the equation, and the fitting
curves of “ln (A /A )–Time” are given in Fig. 7. The slope of straight line after fitting is the
0
t
-4
photo-degradation reaction rate constant, and the “k” values of P1 and P2 are kP1 = 4.8×10
-4
mol/min and kP2 = 1.1×10 mol/min, respectively (Table S3). Obviously, an enhanced
photo-stability effect is obtained via the addition of diallyl-POSS into organic light-emitting
material. Although the specific photo-stability enhancement mechanism is still unclear, it could be
owing to the inorganic POSS nanoparticles, which is unfavorable towards photo-oxidation and
stable against oxidation [25].
3
.4.4. Decoupling Effect of the Hybrids under the State of Aggregation
Absorption spectra and fluorescence emission spectra of polymers in good/poor mixed solutions

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were tested to explore the effect of aggregation for optical polymers according to the method
reported in the literature [26]. In this regard, the polymers can form aggregations and excimers in
THF/water solvents by adding different proportions of water. The absorption spectra and
fluorescence emission spectra of P1 and P2 in THF and in mixed THF/water solvents were
recorded.
Fig. 8. Partial absorption spectra of a) P1, b) P2 and photoluminescence spectra of c) P1, d) P2 in THF, THF–
water (3:7, v/v), and THF–water (1:9, v/v).
As shown in Figure 8a and 8b, both P1 and P2 molecular chains can be well-dispersed in the
dilute THF solution due to the weak intermolecular interaction. Nevertheless, the absorbances at
λmax of P1 and P2 are obviously enhanced and undergo red shift with the increase of water content
(3:7 v/v and 1:9 v/v THF–water), which indicates that the two polymers have formed J-type
aggregations [27].
On the other hand, the conspicuous emission quenching of P1 by adding different proportions
of water in THF were observed. The excimer peak at 482 nm in the P1 emission spectra appeared
clearly in a 1:9 (v/v) THF–water mixed solvent [Figure 8(c)]. The fluorescence emission intensity
of P2 in 3:7 (v/v) and 1:9 (v/v) THF–water is much greater than that of P1, and the emission
spectra of P2 still has no excimer peak in a 1:9 (v/v) THF–water mixed solvent [Fig. 8(d)]. These

ACCEPTED MANUSCRIPT
results indicate that the optical property of P2 is stable in THF/water solvents owing to the
incorporation of diallyl-POSS, while that of P1 is not.
Simultaneously, the QY values of P2 are 23.8% and 12.3% in 3:7 (v/v) and 1:9 (v/v) THF–
water mixed solvent respectively, which are much higher than those of P1 (10.6% and 4.9%, Table
S1). It suggests that the strong dipole–dipole and π–π stacking interactions between organic
optical chromophoric groups can lead to forming J-type aggregations, which would affect
luminescent properties and application of light emitting polymers. Therefore, the incorporation of
“
huge” and “rigid” diallyl-POSS into optical materials via chemical bonds to form bead-type
condensation polymer can effectively improve the optical performances under the state of
aggregation.
3
.5. Fluorescent Composite Film
The fluorescence composite films of P1 and P2 were prepared, and the purpose of which was to
lay the foundation for the application of difunctional-POSS based polymer in developing new
photoelectric material. In this paper, fluorescence composite films were fabricated using the
3
-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and poly-caprolactone diol (PCL
M 1000) as matrix, and doped with different proportions of light-emitting polymer molecules
w
(
Fig. 9). The influence of doped mass fraction of P1 and P2 on PL spectra of the fluorescent
composite films was investigated to elucidate the effect of incorporation of diallyl-POSS into
luminescent material (Fig. 10). Meanwhile, the QYs of fluorescent composite film with different
doped mass fractions of P1 and P2 were measured, and photoluminescence spectra were also
obtained (Table S4). There was no obvious change for PL spectra when the mass fractions of P1
-6
-6
and P2 were 1×10 and 5×10 . The maximum emission peaks of P1 and P2 were both located at
4
27 nm, which are similar to P1 and P2 in dilute solution. This phenomenon shows that the
aggregation of fluorescent groups does not appear when the fluorescence composite films doped
with low mass fraction of P1 and P2.

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Fig. 9. a) Schematic illustration of preparation of fluorescent composite films (taking P2 for example); b) The
-
5
-4
fluorescent composite film doped with 5×10 mass fraction of P1 and 1×10 mass fraction of P2 under sunlight
and 365 nm UV-light.
Compared with fluorescent composite films of P2, the emission spectra of P1 fluorescent
composite films showed larger red shift and more excimer peaks in longer wavelength with the
increase of the mass fraction of P1. It reveals that a more serious aggregation effect of fluorescent
groups has occurred in the fluorescent composite films of P1. Furthermore, the intensity of
excimer emission peak at 535 nm increased dramatically when composite film doped with higher
-3
-3
mass fraction of P1 (1×10 and 5×10 ), while the composite film of P2 merely showed a weak
shoulder peak at 535 nm under the same conditions. This is a powerful evidence to demonstrate
that the strong dipole–dipole and π–π stacking interactions between organic optical chromophoric
groups are suppressed owing to the introduction of diallyl-POSS.
Meanwhile, the maximum QY of P1 fluorescent composite film was 18.8% as doped with
-5
-4
5
×10 mass fractions of P1, while that of P2 was 20.5% as doped with 1×10 mass fractions of
P2. Namely, the maximum QY of the fluorescent composite film of P2 appears at higher doped
-4
-5
mass fraction (1×10 ) than that of P1 fluorescent composite film (5×10 ), which insinuates that
the incorporation of “huge” and “rigid” diallyl-POSS could prevent excessive aggregation in solid

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state. The diallyl-POSS bridged polyfluorene hybrid material with symmetrical structure has
higher QY.
Fig. 10. The PL spectra of fluorescent composite films with different mass fractions of a) P1 and b) P2.
No microphase separation was observed when QYs of fluorescent composite films of P1 and P2
reached the maximum (Fig. 9 and Fig. S2), and the fluorescent composite films of P1 and P2
showed excellent TPF property and could be applied in real-time 3D high-resolution TPF imaging
(
Fig. S3).
4
. Conclusion
In summary, a bead type and diallyl-POSS based polyfluorene (T D type) with high
8
2
symmetrical structure (P2) was synthesized via Heck coupling reaction. The molecular weight of
P1 and P2 was well controlled to provide the polymers with good solubility and process ability.
The HRTEM micrographs showed that diallyl-POSS was uniformly nano-dispersed in the polymer
matrix. And the thermal decomposition temperature (T , 5% loss) increased from 321 °C for P1 to
d
3
82 °C for P2.
Simultaneously, the well-controlled conjugated length gave P1 and P2 with high QYs, and
cooperating “rigid”, “symmetrical” and “huge” diallyl-POSS could further enhance quantum
efficiency in solution and solid state. The rate constants of photo-degradation reaction under a
-4
-4
1
000 W iodine–tungsten lamp were kP1 = 4.8×10 mol/min and kP2 = 1.1×10 mol/min,
respectively, which confirmed the significantly enhanced photo-stability by adding unfavorable
photo-oxidation diallyl-POSS to emissive conjugated polymer. Moreover, a better TPF property
was found for P2, which could also be attributed to the incorporation of diallyl-POSS, and the

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strong dipole–dipole and π–π stacking interactions between organic optical chromophoric groups
could be inhibited. Finally, fluorescent composite films were prepared, and the maximum QY of
P2 reached to 20.5%. These results suggest that bi-functional POSS based polymer may be
considered a class of compounds/materials with anticipated novel properties of value in
developing new components for electronic and photonic applications.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant
No.21104032), the Natural Science Foundation of Jiangsu Province (No. BK2011413), the
Fundamental Research Funds for the Central Universities (No. 1104020505) and the Postgraduate
Research and Innovation Project of Jiangsu Province (2014, No. KYLX_0030). The authors
would like to thank the Program for Changjiang Scholars and Innovative Research Team in
University for financially supporting this research.
Appendix. Supplementary material
Supplementary data related to this article can be found online.
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Supplementary data for
New Bead Type and High Symmetrical Diallyl-POSS Based
Emissive Conjugated Polyfluorene
a,b
a,b
a,b
a,b
a,b
c
b
Jin Huang, Weina Wang, Jiangjing Gu, Weizhi Li, Qiuhong Zhang, Yin Ding, Kai Xi,
a
*,a,b
Youxuan Zheng, Xudong Jia
a
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, Nanjing
University, Nanjing 210093, PR China
b
Department of Polymer Science & Engineering, Nanjing University, Nanjing 210093, PR China
c
State Key Laboratory of Analytical Chemistry for Life Science, Nanjing University, Nanjing 210093, PR China
*
correspondence to: Xudong Jia (jiaxd@nju.edu.cn)
1
. Morphology observation
Fig. S1. AFM height images, phase images and 3D image of P2.

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Fig. S2. The scanning electron microscopy (SEM) image of blank sample (IPDI+PCL1000) a) and b), the mass
-
5
-4
fraction of 5×10 P1 c) and d), and the mass fraction of 10 P2 e) and f) fluorescent composite film.
-
5
-4
Fig. S3. Two-photon fluorescence imaging of P1
(the mass fraction of 5×10 ) and P2 (the mass fraction of 10 )
fluorescent composite film.
2
. Fluorescence quantum yield (Ø) measurements

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Fluorescence quantum yield (Ø) of P1 and P2 was obtained by the following steps. Quinine
sulfate was dissolved in 0.1 M sulphuric acid (literature quantum yield 0.54 at 360 nm) as
1
reference. Then UV-vis absorption and PL emission spectra (with 360nm excitation) of P1 and P2
with different solvent and reference were measured respectively. The accurate Ø value was
calculated according to the given equation:
Isam ꢆ ꢊꢊꢋꢏ
ꢌꢍꢎ
ꢏ
ꢇꢈꢉ
∅ꢀꢁꢂ
= ∅ꢃꢄꢅ
ꢐꢇꢈꢉꢊꢆꢌꢍꢎꢊꢋ
ꢇꢈꢉ
“
Sam” and “ref” refer to sample and reference respectively. “Ø” means quantum yield. “I”is
the integrated emission intensity, and could be calculated from the emission spectra at 360nm
excitation. “A” represents UV-vis absorbance at 360 nm and was control under 0.05 in the 10 mm
quartz to avoid re-absorption effect. “n” is the refractive index.
Table S1. Fluorescence quantum yield (
Ø
) calculation of the fluorescent for deaggregation effect of the
Hybrids.
Sample
Intergrated emission UV Absorbance (A)
intensity (I)
Refractive index of Fluorescence
solvent (n)
quantum efficiency
(Ø)
Quinine sulfate
P1 THF
120647590
197462540
0.0112
1.33
54.0
0.0156
0.0321
1.41
1.36
71.3
10.6
P1 water content 64703405
0 %
P1 water content 39925305
0 %
P2 THF
P2 water content 151783080
0 %
P2 water content 10910340
0 %
7
0.0418
1.34
4.9
9
179073260
0.0130
0.0334
1.41
1.36
77.6
23.8
7
0.0450
1.34
12.3
9