Terpolymers from Borane-Initiated Copolymerization of Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected Light Emission

Article abstract of DOI:10.1002/anie.201901094

The first synthesis of well-defined poly[(phenylmethylene-co-methylpropenylene)-b-methylene, [(C1-co-C3)-b-C1], terpolymers was achieved by one-pot borane-initiated random copolymerization of ω-methylallyl (C3 units, chain is growing by three carbon atoms at a time) and benzyltriphenylarsonium (C1 units, chain is growing by one carbon atom at a time) ylides, followed by polymerization of sulfoxonium methylide (C1 units). Other substituted arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4-fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium. The obtained terpolymers are well-defined, possess a predictable molecular weight and low polydispersity (M_n,NMR=1.83–9.68×10³ g mol^?1, ?=1.09–1.22). An unexpected light emission phenomenon was discovered in these non-conjugated terpolymers, as confirmed by fluorescence and NMR spectroscopy. This phenomenon can be explained by the isomerization of the double bonds of allylic monomeric units along the chain of the terpolymers (isomerization-induced light emission).

Full text of DOI:10.1002/anie.201901094

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Accepted Article
Title: Novel Terpolymers from Borane Initiated Copolymerization of
Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected
Light Emission
Authors: Nikos Hadjichristidis and De Wang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201901094
Angew. Chem. 10.1002/ange.201901094
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http://dx.doi.org/10.1002/ange.201901094

10.1002/anie.201901094
Angewandte Chemie International Edition
COMMUNICATION
Novel Terpolymers from Borane Initiated Copolymerization of
Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected
Light Emission
De Wang*[a] and Nikos Hadjichristidis*[b]
Abstract: We report the first synthesis of well-defined
poly[(phenylmethylene-co-methylpropenylene)-b-methylene, [(C1-co-
C3)-b-C1], terpolymers via one-pot borane initiated random
copolymerization of ω-methylallyl (C3 units, chain is growing by three
carbon atoms at a time) and benzyltriphenylarsonium (C1 units, chain
is growing by one carbon atom at a time) ylides, followed by
polymerization of sulfoxonium methylide (C1 units). Other substituted
arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4-
hope of obtaining poly(substituted methylene).4 Although the
homopolymerization of substituted sulfoxonium ylides were
unsuccessful (due to the steric hindrance around boron centers),
however, the copolymerization of these subsituted ylide
monomers with sulfoxonium methylide was successful. Limited by
the synthetic difficulty and diversity of sulfoxonium ylides, the
development of new ylide monomers in boron-catalyzed
polymerization was highly demanded.
fluorobenzyl)triphenyl
can
also
be
used
instead
of
In 2003, Mioskowski et al reported that 2-methylallyltriphenyl
arsonium ylide is compatible with borane initiated
polymerization.5a However, this monomer did not lead to polymer
substituted on every one carbon atom (C1), but rather on every
three carbon atoms (C3 polymerization), meaning that the chain
is growing by three carbon atoms at a time. In 2005, the same
benzyltriphenylarsonium. The obtained terpolymers are well-defined,
possess a predictable molecular weight and low polydispersity (Mn,NMR
= 1.83-9.68×103 g /mol, Đ = 1.09-1.22). An unexpected light emission
phenomenon was discovered in these non-conjugated terpolymers as
proved by fluorescence and NMR spectroscopy. This phenomenon
can be explained by the isomerization of the double bonds of allylic
monomeric units along the chain of the terpolymers (isomerization-
induced light emission).
authors realized that
a
few others 2-allylsubstituted
triphenylarsonium ylides show the same behavior.5b Later,
Mioskowski et al discovered that by using a non-substituted
allylarsonium ylide as monomer a C1/C3 random copolymer was
obtained, whereas by using terminal dimethyl substituted allylic
arsonium ylide a C1 homopolymer was obtained.6 They explained
the differences by using sigmatropic rearrangement arguments.
Encouraged by this work, our group discovered that 3-
Boron compounds have been used as initiators in the
polymerization of dimethylsulfoxonium methylide, a living C1
polymerization (chain is growing by one carbon atom at a time)
discovered by Shea et al and coined the name
polyhomologation.1 This polymerization, leading to well-defined
ω-hydroxyl polymethylene (PM, equivalent to polyethylene), was
used to synthesize PM-based homo- and block copolymers with
different topology (linear, star, cyclic, etc).2 Our group was also
used polyhomologation of dimethylsulfoxonium methylide to
obtain well-defined PM-based linear, miktoarm star and brush
copolymers by designing/synthesizing novel borane initiators or
by combining polyhomologation with other living/controlled living
polymerization methods such as anionic, cationic, atom transfer
methylallyltriphenylarsonium
ylide,
a
ω-monosubstituted
allylarsonium ylide, leads also to C3 polymerization. Moreover, by
combining ω-monosubstituted allylic arsonium ylide (C3) with
sulfoxonium methylide (C1) we were able to synthesize well-
defined methylene/3-methylpropenylene block and random
copolymers (Scheme 1, A).7 Encouraging by these discoveries
we started exploring the borane initiating polymerization of other
arsonium ylides hoping to obtain novel polymeric materials with
unprecedented properties (Scheme 1, B).
radical,
ring-opening,
and
ring-opening
metathesis
polymerization.3 Later, efforts were focused in the synthesis of
substituted ylides, such as dimethylaminophenyloxosulfoxoniu
methylide,
diethylsulfoxonium
methylide,
(dimethylamino)tolyloxosulfoxonium
cyclopropylide, with the
[a]
[b]
Associate Professor Dr. De Wang,
Ocean University of China, School of Medicine and Pharmacy,
Qingdao, Shandong Province, 266071, China.
E-mail: wangde@ouc.edu.cn
Professor Dr. Nikos Hadjichristidis
King Abdullah University of Science and Technology (KAUST),
Physical Sciences and Engineering Division, KAUST Catalysis
Center, Polymer Synthesis Laboratory
Thuwal 23955, Kingdom of Saudi Arabia
E-mail: nikolaos.hadjichristidis@kaust.edu.sa
Scheme 1. (A) New C3/C1 diblock copolymers (previous work7); (B)
terpolymers (this work) from arsonium and sulfoxonium ylides.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
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10.1002/anie.201901094
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COMMUNICATION
In this communication, we report the design/synthesis of several
novel non-allylic triphenylarsonium ylides and explore their homo-
and copolymerization with ω-methylallyltriphenylarsonium ylide
using triethylborane as the initiator. Moreover, we report the
synthesis of well-defined diblock terpolymers having C1-co-C3
and PM blocks. These terpolymers despite the fact that they don’t
possess conjugated double bonds emit light. This unexpected
phenomenon, investigated by fluorescence and NMR
spectroscopy, revealed that the isomerization of the double bonds
of the C3 units, leading to conjugated double bonds, is the cause
of the emission. This phenomenon (isomerization-induced light
emission) is not present either in polybutadiene-1,4 or
polyisoprene-1,4 (C4 polymerization, chain growing by four
carbon atoms at a time) since the double bonds, unlike in our C3
polymers, are in every four carbons and thus their isomerization
does not lead to conjugated double bonds.
Scheme 2. General reaction for the synthesis of diblock terpolymers [(PA-co-
PBz)-b-PM].
Table 1. Molecular characteristic and melting temperatures of the synthesized
[(PA-co-PBz)-b-PM) diblock terpolymers
We first synthesized benzyltriphenylarsonium tetrafluoroborate
salt (Scheme S1 and Figure S1-S4, ESI), which can be
transformed to benzyltriphenylarsonium ylide monomer, by
treatment with n-butyllithium. The homopolymerization of
benzyltriphenylarsonium ylide with triethyl borane was failed due
to the steric congestion around the boron complex. The
copolymerization of benzyltriphenylarsonium ylide and
sulfoxonium methylide with triethylborane was also unsuccessful,
even after refluxing the mixture of monomers for 3 days (pH>7.0,
phenolphthalein indicator) due to the same steric reason. In
contrary, the copolymerization of benzyltriphenylarsonium ylide
with 3-methylallyltriphenylarsonium ylide was successful because
the 1,3-sigmatropic rearrangement releases the steric hindrance
around boron. The general reactions for the synthesis of
poly[(methylpropenylene-co-phenylmethylene)-b-methylene]
terpolymers [(PA-co-PBz)-b-PM] are given in Scheme 2.
Treatment of benzyltriphenylarsonium and allyltriphenylarsonium
tetrafluoroborate salts in tetrahydrofuran (THF) with n-butyllithium
at -78 oC under argon, resulted in a clear red solution proving the
in situ generations of the corresponding ylide monomers. The red
solution was allowed to warm up to room temperature slowly
(about 2 hours), and then triethylborane was added, followed by
heating at 60 oC for two hours. A clear colorless and neutral
solution (pH=7.0, the absence of monomer) was obtained and
used to initiate the polyhomologation of sulfoxonium methylide at
80 oC for twenty minutes until the solution became neutral
(pH=7.0). The terpolymers (PA-co-PBz)-b-PM were obtained
after oxidation/hydrolysis with trimethylamine N-oxide dihydrate
(TAO.2H2O) [Scheme S3, ESI]. The 1H NMR spectrum of sample
corresponding to polymer 3 (Table 1), a representative example,
clearly shows the signals of the corresponding monomeric units
(Figure S5, ESI). The aromatic protons are appeared at 7.10-7.41
ppm, the peak at  = 5.40 ppm assigned to the allylic double bond
protons, the aliphatic protons are appeared at 1.11–1.65 ppm and
2.51-2.83 ppm, in agreement with the previous report.7 The chain-
end protons assigned to –CH2– connected to the hydroxy group
at  = 3.66 ppm can be used to calculate the degree of
polymerization. The peak at 970 cm-1 (FT-IR spectrum) indicates
that the double bonds (C3 segment) possess the E-configuration
(trans), and the two peaks at 699 and 758 cm-1 further indicate the
aromatic ring (phenyl group) existence (Figure S6, ESI).
The molecular characteristics of three more terpolymers (1, 2 and
4, Table 1) synthesized following the same general procedure
described previously, are given in Table 1 and the corresponding
GPC traces in Figure 1A. It is clear that the synthesized
terpolymers (Mn, NMR = 1.83-9.68×103 g/mol) posses monomodal
and narrow GPC traces (Đ = 1.09-1.17). In addition, a clear shift
of the elution peak from low to high molecular weight was
observed, in accordance with the increased degree of
polymerization (DP) as determined by NMR. The DPNMR of PM is
higher than the calculated values and this could be attributed to
the oxidation/decomposition of a part of the 3-arm boron
macroinitiator during the addition of sulfoxonium methylide.3,7 The
DSC traces of the diblock terpolymers are shown in Figure 1B.
For the low molecular weight (Table 1, entry 1, Mn, NMR = 1.83×103
g/mol) terpolymer, the melting temperature (Tm) corresponding to
PM is 89.4 oC with a crystallinity of about 44%. By increasing the
molecular weight (Table 1, entries 2-4, Mn, NMR = 4.17-9.68×103
g/mol) of PM, the melting temperature (Tm) increases to 114.9 oC,
as expected, with a slight decrease of crystallinity (29-35%). It
seems that the existence of the “soft” segments (C3 and
substituted C1 segments) exercises a small influence on the
crystallization.8
Figure 1. (A) HT-GPC traces (TCB at 150 oC, PS standard); (B) DSC traces
of terpolymers under nitrogen at a heating rate at 10 oC/min.
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Having shown that the benzyltriphenylarsonium ylide can be used
as substituted C1 monomer in the copolymerization with ω-
methylallylarsonium ylide initiated with triethylborane, we
synthesized and investigated other substituted ylides such as
peak centered at 473 nm upon photoexcitation (Figure 3A). The
no emission of monomers (all arsonium ylides used in this paper)
or the related compounds (triphenylarsine or triphenylarsine
oxidizer) excludes the potential contaminant effect and further
confirm the emission comes from the terpolymer (Figure S11,
ESI). The associated UV-Vis spectra reveal an absorption peak
at 295 nm, proving the existence of the phenyl rings and
conjugated double bonds (Figure 3B). As shown in Figure 3C, the
solutions of the four terpolymers in TCB (cloudy at room
temperature because of insolubility of PM) emit blue light under
UV light (365 nm) irradiation. Similar photoluminescence behavior
was also found in bulk sample and film (Figure S12, ESI).
Copolymers 5-7 also shown a similar light emission phenomenon
under UV light irradiation (Figure S13, ESI).
propyltriphenylarsonium,
(3-methylbut-2-en-
1yl)triphenylarsonium and (4-fluorobenzene)triphenylarsonium
ylide (Figure S7-8, ESI). For the synthesis of the corresponding
terpolymers 5-7 (monomer to initiator mole ratio was
[MAs,R]/[[ MAs,Allyl]/[ MS]/[[I] = 17/17/100/1), the same procedure as
of terpolymer (PA-co-PBz)-b-PM was followed. The 1H NMR
spectra displayed the expected signals corresponding to the two
arsonium ylides and sulfoxonium methylide (Figure S9-10, ESI).
The molecular weights of terpolymers 5-7 were determined by 1H
NMR end group analysis (Mn
=
4.3-9.1×103 g/mol) and
polydispersities were detected by HT-GPC with polystyrene as
standards (Đ = 1.16–1.22). The HT-GPC traces were monomodal
with narrow dispersity, proving that our strategy is efficient and
powerful for the construction C1/C3 terpolymers (Figure 2A).
Representative 1H NMR, 19F NMR spectra, corresponding to
polymer 7, are shown in Figure 2B. The peak at  = -116.39 ppm
(19F NMR) further proving the introduction of substituted C1
segment to polymer chain.
After careful study of the structure of the copolymers, we
concluded that the unexpected fluorescence phenomenon most
probably induced by isomerization (isomerization-induced
emission) of allylic double bond. The allylic double bond
isomerization is driven by either light or heat. To prove that we
placed the NMR tube, containing the terpolymer (PA-co-PBz)-b-
PM (polymer 3 was used in this case) in deuterated 1,1,2,2-
tetrachloroethane-d2 (CDCl2CDCl2), under UV light for 5 days.
The proton of the allyl ( = 5.4 ppm) became broad and shifted to
low magnetic field area, indicating the existence of conjugation
(Figure 4A). The PL spectra clearly show that the fluorescence
intensity increased remarkably after 5 days irradiation under UV
light (Figure S14, polymer 7 was used in this case). We also test
the temperature effect, by heating the terpolymer 7 in CDCl2CDCl2
for 24 h at 90 oC, no remarkable changes were detected in both
1H NMR and PL spectra (Figure S15, ESI). These results indicate
that the terpolymer is a light-sensitive but thermodynamics stable
polymer. The homo C3 polymer (polymer 8, for synthesis see our
1
previous work,7 for the H NMR see Figure S16, ESI), gave an
emission at 450 nm in THF solution (Figure 4B). Another two
homopolymers (polymer 9 and 10) obtained by polymerization of
reported allylic arsonium ylide5a, 6 have similar emission behavior
1
(Figure S17, ESI). The H NMR of C3 polymer 8 compared with
UV irradiated one also showed a clear isomerization phenomenon
(Figures S18, ESI). All above evidence proved that the light-
induced isomerization plays a key role in the light emission
phenomenon.
Figure 2. (A) Synthetic route to terpolymers 5, 6, 7 and their HT-GPC traces
(TCB, 150 oC); (B) 1H NMR Spectra of terpolymer 7, inset is the 19F NMR of
the terpolymer (1H NMR and 19F NMR at 600 MHz in CDCl2CDCl2 at 90 oC).
Then, we investigated the non-conjugated terpolymer
fluorescence properties since we thought that potential π-π
stacking (aromatic phenyl rings) in molecular crystals or
aggregates may produce emission.9 To our surprise, the
photoluminescence (PL) of terpolymer 3 showed a clear emission
Figure 3. (A) PL spectra of diblock terpolymer 3 (Table 1) in toluene.
concentration: 3 mg/mL. Excitation wavelength: 342 nm; (B) UV-Vis spectrum
of diblock terpolymer 3 (Table 1) in toluene; (C) Photographs of polymer in 1, 2,
4-trichlorobenzene (TCB) taken at UV (365 nm) light and daylight.
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10.1002/anie.201901094
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Keywords: Arsonium ylides, sulfoxonium ylide, borane,
copolymerization, photoluminescence.
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Figure 4. (A) Proposed mechanism of isomerization and 1H NMR proof under
UV irradiation (365 nm) and (B) PL spectrum of homopolymer 8 (C3 polymer),
the inset is polymer 8 in THF under daylight or UV light (365 nm). Concentration:
2 mg/mL, Excitation: 342 nm.
[3]
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In summary, a novel method for construction of well-defined
C3/C1 containing diblock terpolymers by copolymerization of two
arsonium ylides followed by sequential copolymerization of
dimethylsulfoxonium methylide was successfully reported for the
first time. The successful application of substituted arsonium
ylides as C1 building blocks will widely extend the boron-
catalyzed polymerization of ylide chemistry. An unexpected light
emission phenomenon of this non-conjugated terpolymer has
been observed for the first time. The light emission can be
explained by the formation of short conjugated sites along the
chain under irradiation. We believe that these C3/C1 copolymers
belong to a new family of polymeric materials with interesting
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Corresponding authors
*E-mail: nikolaos.hadjichristidis@kaust.edu.sa
*E-mal: wangde@ouc.edu.cn
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ORCID
De Wang: 0000-0002-3737-6621
Nikos Hadjichristidis: 0000-0003-1442-1714
Acknowledgments
The research reported in this publication was supported by King
Abdullah University of Science and Technology (KAUST).
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COMMUNICATION
COMMUNICATION
The first synthesis of well-defined
De Wang*[a] and Nikos
Hadjichristidis*[b]
poly[(substituted
methylene-co-
propenylene)-b-methylene)]
Page No. – Page No.
terpolymers via borane-initiated
copolymerization of arsonium and
sulfoxonium ylides is presented. An
Novel Terpolymers from Borane
Initiated Copolymerization of
unexpected
phenomenon,
light
due
emission
to the
Triphenyl
Sulfoxonium
Arsonium
Ylides:
and
An
isomerization-induced emission of
the double bonds of the
propenylene units was discovered
Unexpected Light Emission
in
these
non-conjugated
terpolymers.
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