Reviews
ChemistrySelect doi.org/10.1002/slct.202004194
z Materials Science inc. Nanomaterials & Polymers
Developments in the Components of Metal-Free
Photoinitiated Organocatalyzed-Atom Transfer Radical
Polymerization (O-ATRP)
Pritish. S. Aklujkar and Adarsh. R. Rao*[a]
The evolution of the atomic transfer radical polymerization
(ATRP) has instigated an increased demand for designing
versatile and tailored polymeric structures. However, the use of
metal catalysts in traditional ATRP limits the use of polymers in
many niche applications. The recent advancement in ATRP has
engendered the substitution of metal-catalysts by a more user-
friendly class of organic photoredox catalysts, which offer
enhanced control over the polymerization reaction as these
compounds can be easily activated and deactivated with just a
source of light. These new photocatalysts have transformed the
1. Introduction
The rise of free radical polymerization during the early 1980s
can be considered commercially beneficial for the synthesis of
high molecular weight polymers; this rising demand can be
attributed to the favorable reaction conditions and the ease of
performing the reaction on an industrial scale.[1,2] However, the
drawbacks of free radical polymerization like loss of control
over the molecular weight distribution and polymer structure
posed a challenge for future development in the field. This
challenge further led to the development of more advanced
controlled radical polymerization (CRP) techniques, which
enabled an enhanced control over the molecular weight
distribution of polymers.[3–6] The CRP’s fundamental character-
istic, which allows such targeted and controlled growth of the
polymer chain, is the presence of equilibrium between the
propagating and the inactive (dormant) species. Under suitable
kinetic conditions, this equilibrium leads to the continuous
growth of the polymer chain with activation and deactivation
occurring in a controlled manner.[7] The following can be
considered as the features of CRP -
1. Follows first-order kinetics.
2. Yields polymers with narrow molecular weight distribution.
3. Requires fast initiation at low monomer conversion.
4. Targeted degree of polymerization.
5. Low concentration of propagation radicals.
6. Retention of the chain-end group.
7. Linear and increasing molecular weight as a function of
monomer conversion.
[a] P. S. Aklujkar, Dr. A. R. Rao
Department of Polymer and Surface Engineering,
Institute of Chemical Technology, Matunga East, Mumbai- 400019, India
E-mail: ar.rao@ictmumbai.edu.in
ChemistrySelect 2020, 5, 14884 – 14899
traditional ATRP to a metal-free photoinitiated organocatalyzed
– ATRP (O-ATRP), which has potential applications in the
medical and electronic sectors. This review covers the reductive
and oxidative quenching mechanism of the metal-free photo-
induced O-ATRP reaction and the function of each component
to establish a successfully controlled polymerization reaction.
The scope for each component has been encompassed in the
study, which paves the way for future developments in the
field.
8. Initiator efficiency around 100 %.
9. Suppression of termination reactions.
The different types of CRPs are distinguished based on the
type of the reversible-deactivation equilibrium. Reversible
addition-fragmentation chain transfer polymerization
(RAFT),[8–10] nitroxide-mediated polymerization (NMP),[11,12] and
atom transfer radical polymerization (ATRP)[13,14] are different
variants of CRP. ATRP is one of the most widely studied CRP
due to its versatile nature of reaction resulting in the desired
output over a wide range of monomers. The most important
components of the metal-catalyzed ATRP involves a monomer
which is to be polymerized, an alkyl halide initiator with a
suitable chemical structure which is capable of initiating the
polymerization, and a transition metal complex which acts as
the catalyst controlling the activation and deactivation steps of
the reaction, resulting in a polymers with narrow molecular
weight distribution and well defined structures. The metal-
catalyzed ATRP reaction can be schematically demonstrated, as
shown in Scheme 1.[15] As the name suggests, the ATRP
mechanism involves the transfer of a halogen atom between
the propagating polymer chain and the catalyst. Typically, the
popular and conventional ATRP mechanism involves a copper
catalyst, the CuI linked with the ligand which activates the C X
bond of the alkyl halide initiator which is initially in a dormant
state, extracting the halogen atom and simultaneously generat-
ing an alkyl radical which initiates in combination with the
monomer with a rate constant (kp). The oxidized CuII further
deactivates the propagating chain by transferring the halogen
atom to the growing chain and thus regenerating the catalyst
in original oxidation state and the dormant species. Due to
enhanced control over the reaction, there is very less amount
of radical termination which can be considered negligible (kt).
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 Reviews
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Scheme 1. Reaction scheme of metal-catalyzed ATRP.
As the controlled polymerization progresses with continu-
ous activation-deactivation steps, there is an unwanted accu-
mulation of the CuII species. Hence, the development of new
ATRP techniques further relied heavily on reducing the metal
content. This modification led to the development of different
types of ATRPs. Activators regenerated by electron transfer –
ATRP (ARGETATRP),[16–19] supplemental activation reducing
agent ATRP (SARA-ATRP),[20–22] initiators for continuous activator
regeneration ATRP (ICAR-ATRP)[23–25] are the popular modified
form of the metal-catalyzed ATRP. These modifications signifi-
cantly reduced the use of metal-catalyst to a minor amount.
However, the quest for establishing a metal-free ATRP reaction
was still a hurdle to be encountered.
The introduction of light as an enhancing component in
ATRP was initially developed in combination with the metal
catalysts (Cu, Fe)[26–30] to improve the catalyst functioning. Upon
exposure to irradiation, the catalyst complex transitioned to its
excited state and was further reduced in the presence of
electron-rich species like amines.[31] The efficiency and control
over the reaction were enhanced due to the benefits uncov-
Dr. Adarsh R. Rao received a Ph.D. (Tech)
degree in Polymer Engineering and Technol-
ogy from the Institute of Chemical Technol-
ogy (Deemed University),Mumbai,India. His
doctoral research focused on applications of
atom transfer radical polymerization in poly-
mer blends, nanofibers, and additive syn-
thesis. He currently works as an assistant
professor at the Institute of Chemical Tech-
nology, Department of Polymer and Surface
Engineering, Mumbai, India. His current
research interests include applications of
atom transfer radical polymerization, bio-
based polymers, and applications of nano-
materials.
ChemistrySelect 2020, 5, 14884 – 14899 14885
ered from the light source for the metal catalyst
initiation.[29,32–35] The characteristic of photo-controlled ATRP
enables the reaction to be carried under a feasible set of
conditions that include performing the reaction at room
temperature. It also offers an excess control over the activation-
deactivation mechanism, which leads to the formation of a
well-defined polymer structure.[36,37] Photo-controlled ATRP via
metal photoredox catalysts offers control over the polymer-
ization reaction, resulting in the syntheses of versatile polymer
structures.[38] The eminence of photo-controlled ATRP was
further amplified when few organic photoredox catalysts were
found capable of substituting metal catalysts and propagating
a CRP, resulting in a wide range of polymer structures.[39] These
organic photocatalysts[39,40] offer a distinctive advantage over
the metal catalysts as they open new avenues for applying
ATRP, for example, in electronics where metal contamination is
not permissible. Organocatalyzed ATRP (O-ATRP) requires a
simpler reaction setup, familiar sources of irradiation like
sunlight, LEDs, and bulbs, which are adequate for performing
Pritish Aklujkar completed his undergraduate
degree in Surface Coating and Technology
from the Department of Polymer and Surface
Engineering at the Institute of Chemical
Technology (Deemed University), Mumbai,
India in 2020. His final year thesis under the
supervision of Dr. Adarsh R. Rao involved
research on organocatalyzed – atom transfer
radical polymerization for the development
of various polymers using organic dyes. He
has worked on projects involving dye-sensi-
tized solar cells at the National Chemical Lab
(NCL), Pune, and in developing sustainable
thermochromic coatings at the Defense
Institute of Advanced Technology (DIAT),
Pune.
© 2020 Wiley-VCH GmbH
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ChemistrySelect doi.org/10.1002/slct.202004194
the reaction at room temperature.[41,42] Thus, O-ATRP can be
considered greener and an eco-friendly alternative.[43]
The photoredox cycle initiated by the photocatalyst is
essential for a controlled/living reaction of O-ATRP, which
follows either an oxidative quenching or a reductive quenching
mechanism. The mechanism is presented in the next section of
this review, along with the components and conditions
necessary for the photoredox cycle. In general, the components
of O-ATRP are a monomer, initiator, organic photocatalyst,
solvent, a light source, and when the mechanism is progressed
via a reductive quenching, a sacrificial electron donor is an
additional component included in the system. In this study,
each component‘s scope and the specific requirements for its
inclusion in the overall photoredox cycle are elaborately
discussed. The field of photoinduced metal-free O-ATRP is a
recent discovery with a strong potential for future
advancement.[44,45] This review is valuable in understanding the
current prospects of O-ATRP and a guide for designing superior
components for future variations.
2. Organic Photocatalysts
In the metal-catalyzed ATRP (traditional ATRP), metal catalyst
(Cu (I)) activates the initiator, and the reaction proceeds in a
regulated manner. Specific organic compounds can perform a
role similar to that of the metal catalysts under the stimulus of
light. Their high reduction potential and enhanced topological
and temporal control under irradiation enable them fit for a
controlled polymerization reaction. These organic compounds,
termed as ’Photocatalysts,’ are gaining significant attention in
Figure 1. Chemical structures of different photocatalysts used.
ChemistrySelect 2020, 5, 14884 – 14899
recent times due to their application in the photoinduced O-
ATRP; Figure 1 shows the different photocatalysts commonly
used.
To understand the nature of compounds that can be
suitably used as a photocatalyst in O-ATRP, an understanding
of the O-ATRP mechanism as a whole and the subtle role in the
mechanistic steps is crucial to be recognized initially. The
mechanistic steps involved in the photoinduced metal-free
ATRP rely majorly on the electrochemical properties of the
photocatalyst used. The photoredox cycle, essential in main-
taining a controlled and continuous polymerization reaction,
follows a reductive quenching pathway or an oxidative
quenching pathway.
Initially, the oxidative and reductive quenching mechanisms
were extensively investigated for Atom Transfer Radical
Addition (ATRA) reactions. These ATRA reactions involved
metal-based photocatalysts, which, upon exposure to irradi-
ation, led to the transfer reactions through the quenching
mechanisms. Nguyen et al. performed the ATRA of haloalkanes
and α-halocarbonyls to olefins using Ir[(dF(CF3)ppy)2(dtbbpy)]
PF6 as a PC operated via oxidative quenching mechanism.[46]
This synthesis method proved beneficial for producing efficient
yields under controlled reaction conditions. Expanding the
scope of using metal-based photocatalysts operated through
photoredox cycles, Wallentin et al. studied the ATRA of
haloalkanes onto alkenes and alkynes.[47] In their investigation,
[Ir{dF(CF3)ppy}2(dtbbpy)]PF6 and [Ru(bpy)3]Cl2 were used as the
photocatalysts, which operated via oxidative and reductive
quenching mechanisms, respectively. The study, thus, high-
lighted the use of photocatalysts operated via both mecha-
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nisms. Upon analysis of the products formed, it was found that
the reaction through the oxidative quenching mechanism
produced a more efficient desired product as compared to the
yield via the reductive quenching mechanism. Also, sacrificial
electron donors used in reductive quenching can lead to an
unwanted side reaction. Oxidative quenching works efficiently,
avoiding the use of a sacrificial electron donor. However, there
is a decrease in the PC’s reductive ability in oxidative
quenching, limiting the substrate span for such reactions. This
comparative approach between the mechanisms is helpful in
devising further modifications to the mechanisms.
2.1. Oxidative Quenching Mechanism
Implementation of oxidative quenching was explored in ATRP
initially using the metal-catalysts. Fors et al. developed a
photocontrolled ATRP of methacrylate monomers using fac-[Ir
(ppy)3] as the photocatalyst, which operated via oxidative
quenching mechanism.[35] Simple reaction setups, excess con-
trol over the polymerization, and a lower amount of required
catalyst proved that the photocontrolled ATRP was advanta-
geous for synthesizing methacrylate monomers. Treat et al.
expanded the use of fac-[Ir(ppy)3] as a PC for photoinitiated
ATRP operated via an oxidative quenching mechanism for
polymerizing several acrylates.[48] Ma et al. further investigated
the same photocatalyst in their synthesis of poly(ethylene
glycol) methyl ether methacrylate (PEGMA) and a block
copolymer of PMMA- b –PPEGMA.[49] The advantages of photo-
controlled ATRP are exceptional functional group tolerance and
enhanced controlled polymerization. To avoid metal contami-
nation and establish a cleaner polymer synthesis[50], several
Figure 2. Photoredox cycle of O-ATRP via oxidative quenching mechanism. (Cat = photocatalyst, X = halide atom, M = monomer, Pn-X = initiator, Pn° = alkyl
radical, P(n + m) X = dormant polymer chain).
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organic photocatalysts were further developed for the photo-
controlled ATRP. We further understand the oxidative quench-
ing mechanism and its development in the field of O-ATRP.
Figure 2 describes the photoredox cycle via oxidative
quenching pathway; the steps involving O-ATRP via an
oxidative quenching pathway can be highlighted as follows –
1.) Excitation of photocatalyst upon exposure to light in a
specific range of wavelengths.
2.) Activation of the alkyl halide initiator (Pn X) leads to the
generation of propagating species (alkyl radical + mono-
mer) and simultaneous formation of the photocatalyst
radical cation halide anion complex.
3.) Deactivation via a reversible redox reaction between the
photocatalyst-halide complex and propagating polymer
chain.
4.) Thus, the photocatalyst is regenerated, and the polymer is
end-capped by the halide atom at the end of each cycle.
The oxidative quenching mechanism for O-ATRP can be
briefly discussed as follows – Upon exposure of the photo-
catalyst (PC) to irradiation, the PC transitions from its ground
state singlet to a singlet excited state. From the singlet excited
state, the photocatalyst may return to its ground state directly
by exhibiting fluorescence (a radiative pathway) or move to a
triplet state via intersystem crossing (a non-radiative pathway)
and then return to the ground state.[50] The triplet state has a
comparatively longer lifetime than the singlet excited state.[51]
Initial mechanistic reports suggested that the triplet excited
state and the charge transfer character play a significant role in
controlling the polymerization.[52] But, recent reports suggest
that the singlet excited states, although short-lived, enhances
the control over the polymerization, and the molecular weight
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distribution of the product can be controlled more efficiently.
In a recent report, Koyama et al. investigated the oxidative
quenching mechanism.[53] The O-ATRP using photocatalysts
N,N-diaryl-5,10-dihydrophenazines was examined in their study.
Their work indicated that the singlet-excited state repressed
the concentration of the debrominated radical. The debromi-
nated radical can lead to an unwanted side reaction due to its
reactive nature, and its suppression thus results in enhanced
control over the polymerization reaction. Hence, the results
indicate that the formation of a singlet excited state is majorly
favorable for an O-ATRP operating via an oxidative quenching
mechanism. Further, the photocatalyst in its excited state gets
oxidized to a radical cation (PC° +), reducing the alkyl halide
initiator (Pn X) to an alkyl radical (Pn°) and halide anion (X ). In
their mechanistic study, Pan et al. demonstrated the formation
of a complex between PC radical cation and halide anion (PC° +
X ). This complex was found to be in equilibrium with the
PC° +. The electron transfer between PC° + and the complex
(PC° + X ) resulted in the transfer of halide anion to the end of
the expanded polymer chain (P(n + m)X) and the PC to its ground
state, thus ending one photoredox cycle (Figure 2).[54]
With the knowledge of the oxidative quenching mecha-
nism, we can further extend our understanding in classifying
the organic compounds which perform along the specified
steps to accomplish an O-ATRP reaction. What type of organic
compounds can be utilized as efficient photocatalysts for O-ATRP?
Remains a fundamental question in the context of developing
novel photocatalysts and understanding the ones currently in
use. Upon investigation of the above mechanism, it is evident
that the organic compounds, when are activated by light, must
immediately transition to a stabilized excited state. The excited
states must have the required reduction potential to efficiently
activate the initiator and have sufficient lifetime to render the
reaction cycle. The photocatalyst radical cation formed after
activating the initiator must capably deactivate the polymer-
ization and end one polymerization cycle. A perspective into
the electrochemical nature of a suitable photocatalyst can be
grasped through the research conducted by Daniela M. Arias-
Rotondo and James K. McCusker,[51] and also an insightful study
by Theriot et al. on the designing of photocatalysts preferable
for oxidative quenching offer potential prospects for the further
study into photocatalysts.[39]
2.2. Classification of O-ATRP Photocatalysts Operating via
Oxidative Quenching:
Phenothiazine derivatives are one of the earlier discovered
photocatalysts for the photoinduced metal-free O-ATRP, Treat
et al. synthesized and studied the effect of 10-phenylpheno-
thiazine in the O-ATRP of methyl methacrylate, dimeth-
ylaminoethyl methacrylate (DMAEMA), and chain expansion
with benzyl methacrylate (BnMA) under 380 nm of UV exposure
at room temperature.[55] The alteration in the initiator to
monomer ratios enabled the researchers to synthesize poly-
mers with narrow molecular weight distribution, and further
synthesis of block copolymers was also possible. Pan et al., in
their study, reported the use of phenothiazine derivatives, 10-
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(4-methoxyphenyl)-phenothiazine (4-MeOPh-PTZ) and 10-(1-
naphthalenyl)-phenothiazine (Nap-PTZ), for polymerizing acryl-
onitrile through photoinduced O-ATRP.[56] The concentrations
of varying monomer, photocatalyst, and initiator led to
polymers with narrow molecular weight distribution. The end-
capped PAN obtained was further used to synthesize the PAN-
b-PMMA block copolymer. Further research by Dadashi-Silab
et al. led to phenyl benzo[b]phenothiazine (Ph-benzoPTZ) as a
photocatalyst for polymerizing different methacrylate mono-
mers in the presence of a 392 nm visible light LED.[57] The 10-
phenyl phenothiazine derivative can also be used for photo-
initiated dehalogenation of different alkyl halides at room
temperature in the air.[58,59] Thus, phenothiazine derivatives can
be considered one of the significant classes of photocatalysts
widely studied due to their effectiveness in achieving an O-
ATRP through an oxidative quenching mechanism.
Several polycyclic aromatic hydrocarbons are excellent light
absorbers which exhibit strong fluorescence.[39] Miyake and
Theriot successfully achieved polymerization of MMA using
perylene as photocatalyst irradiated under natural sunlight.[60]
Low initiation efficiencies and relatively high Đ can be
considered some of the drawbacks of using perylene. Allushi
et al. comparatively studied the incorporation of anthracene
and pyrene to the O-ATRP of MMA and other vinyl
monomers.[61] Anthracene was capable of gaining a faster
activation of the initiator than pyrene, but pyrene helped
synthesize polymers with superior control over the function-
alities and molecular weight distribution. Perylene was further
investigated by Aydogan et al. to the synthesis of poly(methyl
methacrylate) (PMMA) and polystyrene (PS) hyperbranched
polymers having bromo-functionalities.[62]
Phenoxazines derivatives can be efficient PCs for O-ATRP
reactions. Pearson et al. studied and enhanced the photo-
physical properties of phenoxazine derivatives. A comparative
study performed between phenoxazines, dihydrophenazines,
and phenothiazines as photoredox catalysts showed that
keeping the planar conformation of phenoxazine derivatives
during the catalytic cycle enhances the synthesis of tailored
polymers. The principles established through their study
helped in designing (3,7-di(4-biphenyl) 1-naphthalene-10-phe-
noxazine) as PC, which resulted in optimum performance for O-
ATRP.[63] In their investigation for designing efficient photo-
catalysts by altering the structure, McCarthy et al. modified the
core of the phenoxazine derivatives, resulting in the alteration
of their triplet energy states, oxidation potential, and reduction
potentials. The results showed that the phenoxazine derivatives
with excellent absorption in the visible light having high
reduction potential in their triplet excited state offered
enhanced control over the O-ATRP throughout the reaction.[64]
Through computational investigations, Theriot et al. dem-
onstrated the strongly reducing diaryl dihydrophenazines as
PCs in their research. These PCs could easily activate the
initiator in visible light and helped synthesize tailored struc-
tures through O-ATRP.[65] Cole et al. investigated a class novel
core-substituted N,N-diaryl dihydrophenazines, which were
efficient for O-ATRP at low catalyst loadings (5–50 ppm). The
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computationally designed catalysts proved advantageous for
synthesizing a variety of different polymeric structures.[66]
Recently, a new class of PCs consisting of dimethyl-
dihydroacridines derivatives was developed by Buss et al. for O-
ATRP. The structural modification performed in their study
helped design derivatives, which further led to an efficiently
controlled O-ATRP through the oxidative quenching. The
dimethyl-dihydroacridine PCs were also explored in continuous
flow reactors for synthesizing acrylate polymers with narrow
molecular weight distribution.[67] Expanding the scope of
dihydroacridines as PCs, Liu et al. demonstrated 9,9-dimethyl
dihydroacridine as a potential PC in O-ATRP. By substituting
the PC’s active sites with required substituents, a functional
structure-property relationship was established, which helped
synthesize the DPDHA-P2F2 derivative as PC for efficient O-
ATRP.[68] Various other photocatalysts are also found suitable
for O-ATRP, including the derivatives of thienothiophene[69] and
carbazoles.[70] All the organic compounds discussed so far have
a robust reduction potential in their excited state and an
adequate excited-state lifetime, enabling them to mediate the
polymerization through oxidative quenching mechanism.
2.3. Reductive Quenching Mechanism
Apart from the broadly studied photocatalysts operating
through oxidative quenching mechanism, the development in
the field has also led to the generation of relatively economical
organic dyes that, combined with amines, can lead to O-ATRP,
operating through a reductive quenching pathway. The
reaction cycle in the presence of light can be pictorially
Figure 3. Photoredox cycle involving reductive quenching mechanism: (Cat = photocatalyst, A = amine co-initiator, Pn-X = initiator, X = halide atom, Pn° = alkyl
radical).
ChemistrySelect 2020, 5, 14884 – 14899
depicted, as shown in Figure 3. Extensive research in the
mechanistic aspect of the reductive quenching is limited,
opening doors for the future scope in this field. The computa-
tional studies carried out by Allushi et al. explain the potential
steps in the reductive quenching mechanism discussed further
in this section.[71]
The general steps in the O-ATRP via the reductive pathway
can be summarised as followed: Upon excitation of the
photocatalyst (dye), the PC transitions to the excited state
similar to the shift seen for photocatalysts in the oxidative
mechanism. Further, as shown in Figure 3, the sacrificial
electron donor (A) reduces the dye to a more stable anionic
radical (Cat° ) by donating an electron. The stable anionic
radical of the dye further activates the alkyl halide initiator
(PnX) generating halide anion (X ) and alkyl radical (Pn°), which
further initiates the polymerization. Electron transfer from the
halide anion (X ) to the cationic electron donor radical (A° +)
further leads to the deactivation of the polymerization by
halide radical, and the dormant species are formed with their
chain terminated by halide. Thus, one photoredox cycle is
completed with the PC back to its ground state and dormant
expanded polymer chains. Bian et al. ’s mechanistic study
revealed the importance of the sacrificial electron donor in the
reductive quenching mechanism.[72] It was found that the rate
of polymerization increases with an increase in the concen-
trations of electron donors, which results in a higher concen-
tration of the alkyl radicals (Pn°), which initiate the polymer-
ization. Also, the electron donor concentration was found to
remain constant at the end of the polymerization, suggesting
an electron back transfer from halide to the electron donor
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cation regenerating the sacrificial electron donor at the end of
the photoredox cycle. Thus, the results of the study confirm the
earlier discussed mechanism of O-ATRP through reductive
quenching.
Different compounds have been studied in the recent past,
which can successfully yield a controlled polymerization
reaction through the reductive quenching pathway; these
photocatalysts are discussed further.
2.4. Classification of O-ATRP Photocatalysts Operating via
Reductive Quenching:
Fluorescein was initially studied as a photocatalyst by Liu et al.
for the polymerization of MMA through the photoinduced
electron transfer - ATRP (PET-ATRP).[73] The supplementary role
of triethylamine as an electron donor led the polymerization
through a reductive quenching pathway. Further, Kutahya et al.
developed a dye-amine system using the electron acceptor
dyes eosin Y[74] and erythrosine B, along with amine
(N,N,N’,N’’,N’’ pentamethyldiethylenetriamine), for carrying the
controlled ATRP of MMA under a 400–500 nm light source at
room temperature.[75] The polymer synthesized from these dyes
had narrow molecular weight distribution, and in comparison
to fluorescein, these dyes exhibited enhanced absorption
efficiencies in the projected wavelength range.
The sacrificial electron donor‘s involvement may lead to
side-reactions, which may further result in unwanted free
radical polymerization. The PMDETA amine radical cation may
get converted to amine radical by transferring a proton to the
anionic radical dye (photocatalyst). Thus the control on the
reaction can be lost as amine radical further initiates the
polymerization. There is, thus, competitiveness between the
formation of the alkyl radical and an amine radical, where the
formation of the former favors a controlled polymerization
while the latter resulting in a free radical polymerization
reaction. Allushi et al. studied extensively the reaction kinetics
of the O-ATRP involving reductive type II photocatalysts, which
included benzophenone (BP), thioxanthone (TX), and camphor-
quinone (CQ).[71] The reaction system comprised of type II
photocatalysts, PMDETA, and alkyl halide for polymerizing
various vinyl monomers. Results showed that the thermody-
namics energetically favored the controlled polymerization
reaction for all the photocatalysts. But, for benzophenone, due
to its relatively close values of enthalpies and free energies for
the controlled and free radical polymerization, a broad
Table 1. O-ATRP photocatalysts differentiated based on the quenching mechanism.
Oxidative Quenching Reference
[55]
Phenothiazines
[63]
Phenoxazines
[60]
Perylene
[61]
Pyrene
[69]
Thienothiophene
[65]
Phenazines
[70]
Carbazoles
[68]
Dihydroacridines
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molecular weight distribution of the polymer was seen. Thus, a
selection of PCs based on the difference in their thermody-
namic parameters can be a useful tool in designing novel PCs
for O-ATRP applications. The PC discussed above has broad
absorption spectra, as depicted in Figure 4, which extends the
scope for irradiation sources, which can be used to excite
them. The wavelength of absorption indicates the energies of
the excited states; the longer the wavelength of absorption,
the lesser is the energy of excited states of PC.
The reductive quenching mechanism for the O-ATRP can be
further expanded to polymerize functional monomers like azide
derived monmers.[77] The medical field application includes the
research carried by Liu et al. for implementing metal-free ATRP
for the detection of lung cancer DNA.[76] And an unprecedented
approach for the O-ATRP through a reductive pathway in an
aqueous media was demonstrated by Bian et al., which ensured
a controlled polymerization in the absence of metal and
organic solvent.[72] Various benzaldehyde derivatives can also
be used as photocatalysts; Ma et al. carried O-ATRP using p -
anisaldehyde, p - cyanobenzaldehyde, and 2,4-dimethoxy
benzaldehyde, as photocatalysts in visible-light along with
reductant N, N-dimethylaniline.[77]
Table 1 describes the compilation of photocatalysts based
on their mode of operation. To summarize, the room for
development and scope of the photocatalysts for the O-ATRP is
immense. A greater understanding of the photocatalyst‘s role
in the mechanism of polymerization paves the way for the
synthesis of novel compounds possessing specific properties
required for the reaction. Photocatalysts with higher reduction
potential, higher efficiency, and broader absorption in the
visible region are a prospect for future developments in O-
ATRP.
3. Initiators
The initiator‘s role in ATRP can be understood through the
concepts developed for understanding the kinetics behind
metal-catalyzed ATRP reaction.[13] ATRP rate constant KATRP,
which is kact/kdeact, is generally small for ensuring reasonable
control over polymerization (as kdeact should be higher than
kact). The dependence of KATRP on other components of the
traditional ATRP is shown in Equation 1.[79] The dependence of
molecular weight distribution of polymers synthesized via ATRP
is shown in Equation 2; it is seen that the molecular weight
distribution (Mw/Mn) is dependent on the concentration of
Reductive Quenching Reference
[78]
Eyosin Y
[75]
Erythrosin T
[71]
Benzophenone
[71]
Thioxanthones
[71]
Camphorquinone
[73]
Fluorescein
[77]
Benzaldehydes
– –
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Figure 4. UV- Vis spectra of some type II photocatalysts in DMF. Reproduced with permission from Ref.[59] Copyright 2017 Royal Society of Chemistry.

dormant species (PnX), deactivator (Cu II), the rate constants of
propagation (kp) and deactivation (kdeact), and monomer
conversion (p).
� �
Mo kpkact½Pn X �½CuðIÞ�
ln ¼ (1)
M kdeact½CuðIIÞ�
� �
Mw kp½Pn X �o 2
¼1þ 1 (2)
Mn kdeact½CuðIIÞ� p
The halide atom must efficiently migrate between the
growing polymeric structure and the initiator complex, and if
the initiator is easily activating, the growing chains are constant
and, therefore, equal to the initiator‘s initial concentration. The
degree of polymerization depends on the initial concentration
of the initiator, as shown in Equation 3.[13] The traditional ATRP
initiators are majorly alkyl bromides and alkyl chlorides.
Systems with alkyl bromide initiators have a higher activation
rate as they can be radicalized easier than alkyl chloride as R Cl
bond strength is higher than that of R Br.[80] Alkyl iodides are
generally susceptible to side reactions and are not compatible
with the catalysts; thus, they are not preferred; similarly, alkyl
fluorides-based ATRP is less efficient than the alkyl bromide
and alkyl chloride due to the higher bond strength of alkyl
fluoride initiators.[81]
Thus, for a continuously controlled polymerization to
progress, the initiator should easily activate the polymeric
species. The halogen atom should migrate swiftly and termi-
nate the chain. The initiator should be less active than the
dormant chain so that it does not dimerize before initiating the
propagation.[82]
½M�o
DP ¼ � conversion (3)
½initiator�o
An extensive study on the effect of the initiator in the
metal-catalyzed ATRP can be found in the research published
by Tang et al.[79] Computational analysis on the role of initiator
in ATRP, including the study of electronic transitions involved
and an overall mechanistic understanding, can be grasped by
studying different models developed by Fang et al.[83] For the
photoinduced metal-free O-ATRP, there is a vast scope for
research considering the limited number of initiators prevalent
in the current literature.
Among the many alkyl bromide initiators used for photo
mediated ATRP ethyl α-bromophenylacetate (EBPA) is most

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ChemistrySelect doi.org/10.1002/slct.202004194
widely used owing to its very high activity in the initiation step
and enhanced stability of its radical due to the presence of
benzyl and carboxyethyl groups; figure 5 shows the structure
of EBPA and its stabilized radical. The use of chlorinated
initiators is not favorable for metal-free O-ATRP as it results in
an uncontrolled polymerization.[54]
3.1. Classification of O-ATRP initiators
EBPA as initiator is efficiently utilized along with phenothiazine
derivatives as a photocatalyst to accomplish a successful
polymerization of MMA, AN, and the synthesis of various block
copolymers.[55,56] Discekici et al. demonstrated the interaction of
the photocatalyst 10-phenylphenothiazine (PTH), a phenothia-
zine derivative, with different initiators involving aryl and alkyl
iodides, chlorides, and bromides under different reaction
Figure 5. A = Structure of EBPA, B = Stable EBPA radical participating in the ATRP.
Figure 6. Chemical structure of different initiators used in O-ATRP.
ChemistrySelect 2020, 5, 14884 – 14899
condition, which gives an in-depth understanding of the radical
dehalogenation.[58] In another study, EBPA was found to be the
most efficient initiator for synthesizing polymers with low PDI
from a pool of other initiators, including diethyl 2-bromo-2-
methylmalonate (DEBMM), methyl α-bromoisobutyrate (MBiB),
and ethyl α-bromoisobutyrate (EBiB) for O-ATRP of MMA using
benzo[b]phenothiazine as photocatalyst.[57] Diethyl 2-bromo-2-
methylmalonate (DEBMM) initiator was efficient in polymerizing
PMMA using phenazine and phenoxazine derivatives as a
photocatalyst.[63,84] Initiators like ethyl 2-bromoisobutyrate (EBI),
(1 - bromoethyl) benzene (BEB), and ethyl 2-bromopropionate
(EBP) are found useful along with aromatic photocatalysts like
perylene and anthracene.[61] Aydogan et al. used bifunctional
ATRP initiator, 3- hydroxypropyl 2-bromo-2-methylpropanoate
(HPBIB), for the one-pot synthesis of block copolymers using
simultaneous metal-free ATRP and ring-opening polymerization
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Figure 7. Molecular weight and 1H NMR spectrum of PAN-b-PMMA synthe-
sized from photoinduced O-ATRP. Reprinted with permission from (X. Pan, M.
Lamson, J. Yan, K. Matyjaszewski, 2015, DOI 10.1021/mz500834 g).[47] Copy-
right 2015 American Chemical Society.
(ROP), which signifies the use of functional initiators.[85] Figure 6
shows different initiators with their chemical structure.
When the mechanism of the O-ATRP is operated via a
reductive quenching mechanism, a sacrificial electron donor is
Figure 8. Reaction scheme using biomass-based monomers, the blue part is from biomass. Reproduced with permission from (Wang, J.; Yuan, L.; Wang, Z.;
Rahman, M. A.; Huang, Y.; Zhu, T.; Wang, R.; Cheng, J.; Wang, C.; Chu, F.; Tang, C. Macromolecules 2016, 49, 7709).[73] Copyright 2016 American Chemical Society.
ChemistrySelect 2020, 5, 14884 – 14899
added to the system of components for O-ATRP. The sacrificial
electron donors’ functioning in the photoredox cycle has
already been discussed in the earlier section. N, N, N’, N’’, N’-
pentamethyldiethylenetriamine (PMDETA) is widely used as
sacrificial electron donor when different dyes and type II
photoinitiators are used as photocatalysts along in combination
with alkyl bromide initiators discussed above.[71,75]
Similar to the guidelines established for the photocatalysts
discussed in the previous section, certain conditions can be
estimated to use initiators in the O-ATRP system. A potent
activating initiator results in a controlled polymerization
reaction, and it must be compatible with the photocatalyst and
the propagating chain for the exchange of the halide atom in
between them. Consideration of these conditions thus enables
further scope in the synthesis of initiators compatible with
ATRP. Novel innovations in the field like the synthesis of
hyperbranched polymers using self-condensing vinyl polymer-
ization approach with the help of monomer/inimer pair
comprising of inimers - 2-(2-bromoisobutryloxy) ethyl meth-
acrylate (BIBEM), 4-Vinylbenzyl bromide (VBB) and polymers -
MMA, and polystyrene extend the scope of initiator design for
advanced O-ATRP.[62]
4. Monomer
Monomer in O-ATRP is the most intriguing component; the
expansion and future scope of O-ATRP are strongly inclined
towards polymerizing as many different monomers as possible.
Due to the structural advantage for synthesizing different
copolymers from the polymers synthesized via ATRP, major
research can be found on the chain extension and block
copolymerization of O-ATRP monomers. The most sort after
monomer for O-ATRP are acrylate monomers; major initial
research in the field relies strongly on the polymerization of a
variety of acrylate monomers due to a notable functional group
tolerance offered by O-ATRP. Methyl methacrylate (MMA,
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Figure 9. TEM images of (a) Monodispersed silica microspheres (b) Silica-Supported 2-bromoisobutyryl bromide initiator, (c) and (d) ATRP product - Silica-
Supported Poly 4-vinylpyridine. Reprinted with permission from (A. Ma, J. Zhang, N. Wang, L. Bai, H. Chen, W. Wang, H. Yang, L. Yang, Y. Niu, D. Wei, Ind. Eng.
Chem. Res. 2018, 57, 17417–17429).[77] Copyright 2018 American Chemical Society.
benzyl methacrylate (BnMA), poly (ethylene glycol) acrylate
(PEGA), dimethylaminoethyl methacrylate (DMAEMA), isobutyl
methacrylate (IBMA), and isodecyl methacrylate (IDMA) deriva-
tives are examples of the monomers successfully utilized for O-
ATRP.[55,57,75]
Expanding monomers’ scope, Pan et al. successfully poly-
merized acrylonitrile (AN) using phenothiazine photocatalyst.
The polyacrylonitrile (PAN) was further copolymerized with
PMMA resulting in PAN-b-PMMA block copolymer. Figure 7
shows the molecular weight distribution and the block
copolymer‘s NMR spectrum obtained from photoinduced O-
ATRP.[56] Thus, a system of components operational through
oxidative quenching for the synthesis of PAN was successfully
established. Further, PAN was synthesized using eosin Y as a
photocatalyst and initiator benzenediazonium tetrafluorobo-
rate under visible light by Niu et al., the product showed a high
molecular weight and narrow molecular weight distribution of
polymers.[78] Hence, acrylonitrile is a potential candidate and
can be polymerized via O-ATRP using different photocatalysts.
Due to the current environmental concern worldwide, a
greater emphasis is given to green technology; monomers
from renewable sources and biodegradable polymers are
highly sought after by the researchers. Wang et al. utilized O-
ATRP of biomass-derived methacrylate- monomers, which
ChemistrySelect 2020, 5, 14884 – 14899 14894
included soybean oil methacrylate (SBMA), furfuryl methacry-
late (FMA), and dehydroabietic ethyl methacrylate (DAEMA),
which were derived from the natural source.[86] The study
shows an emphasis on synthesizing polymers and block
copolymers obtained from natural sources and polymerized via
O-ATRP. Figure 8 shows the reaction outline. Lu et al. initially
adapted the metal-free O-ATRP technique to synthesize
cellulose graft copolymers with enhanced properties, synthe-
sized from ethyl cellulose (EC) and biomass-derived monomers
lauryl meth-acrylate derived from fatty acid, furfuryl methacry-
late derived from furfural and rosin monomer.[87] In their recent
study, Lu et al. developed sustainable and recyclable thermoset
elastomers derived from cellulose, fatty acid, and furfural
through the photoinduced O-ATRP and Diels-Alder reaction.[88]
The thermoset elastomers synthesized showed increased
mechanical strength and enhanced elastic properties.
Another prominent scope for monomers can be seen in the
research related to the surface-initiated metal-free O-ATRP,[89]
Ma et al. polymerized 4-vinylpyridine (4VP) via O-ATRP using
Rhodamine B as a photocatalyst for further synthesizing self-
healing nanocomposite hydrogel, Figure 9 shows the TEM
analysis of the microspheres formed.[90] The O-ATRP product
was encapsulated in the surface-modified silica nanoparticles,
where the final product showed improved self-healing proper-
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ChemistrySelect doi.org/10.1002/slct.202004194
Figure 10. Monomers scope in O-ATRP.
ties. Also, the development of single-ion homopolymer electro-
lytes consisting of poly(poly(ethylene oxide) methacrylate
lithium sulfonyl(trifluoromethylsulfonyl)imide), and poly(PEO-
MA-TFSI-Li +) by Li et al. via photoinduced metal-free O-ATRP[91]
and the O-ATRP of methacrylic acid in a continuous flow
reactor, broadens the scope of monomers.[42] Figure 10 com-
piles some of the typical monomers which can be polymerized
via O-ATRP.
5. Solvent and Irradiation Source Scope
In O-ATRP, the use of polar solvents, N,N-dimethylacetamide
(DMA), N,N-dimethylformamide (DMF), and dimethyl sulfoxide
(DMSO) is majorly reported. It is expected that the presence of
a more polar solvent stabilizes the ionic intermediates during
the reaction process. But a detailed study on the solvent‘s exact
behavior with other components involved in the O-ATRP
reaction is yet to be fully understood, which narrows down the
use of solvents used currently to a particular class.
Allushi et al. compared the efficacy of solvents with
increasing polarity. The effect of three solvents, acetonitrile
(ACN), DMF, and DMSO with respective polarity indexes – 5.8,
6.4, and 7.2 on the O-ATRP of MMA using isopropyl
thioxanthone as PC and ethyl α-bromoisobutyrate as initiator
was studied. Increasing solvent polarity showed an increase in
the conversion percentage and decreased PDI of the polymer
formed by O-ATRP.[71] Further, to analyze the solvent and
photocatalyst interaction, Ryan et al. emphasized their work on
the effect of charge transfer character of the PC N,N-diaryl
ChemistrySelect 2020, 5, 14884 – 14899 14895
dihydrophenazine on the solvent polarities. Photocatalysts
exhibiting charge transfer character can be efficient in a wide
range of solvent polarities compared to the photocatalysts not
having charge transfer character.[92] Thus, a perspective for
designing a photocatalyst depending on the use of solvents
and vice-versa can be examined from the study. Figure 11
shows the emission spectra of three diaryl dihydrophenazine
derivatives in different solvents; the solvatochromic response
increasing red-shift emissions is due to the stabilization of the
polar charge-transfer states in highly polar solvents. The
influence of the increasing polarity of solvents on the photo-
catalysts’ charge-transfer character can be analyzed from
figure 11. Expanding the scope of use of a solvent in O-ATRP, a
recent study by Bian et al. demonstrate a metal-free O-ATRP of
poly(ethylene oxide) methyl ether acrylate (PEGA480) using
water as a solvent and Eosin Y as a photocatalyst.[72] Thus, an
excellent room for expanding the O-ATRP solvents in media
other than the polar medium has robust research potential.
Light as a driving source for the reaction mechanism offers
several advantages over previously invented techniques for
ATRP. External control over the catalytic activity enables
enhanced control over the polymerization, and thus, a variety
of different polymers with a narrow molecular weight distribu-
tion inhibiting varying structural characteristics can be
synthesized.[37] Regular sources of light, including LEDs, and
CFLs can be used, and the reaction can also be carried in the
presence of sunlight depending on the nature of the photo-
catalyst used. Figure 12 shows the O-ATRP of MMA using
perylene as a photocatalyst, EBPA as an initiator, and sunlight
© 2020 Wiley-VCH GmbH
 Reviews
ChemistrySelect doi.org/10.1002/slct.202004194

Figure 11. Emission spectra of different diaryl dihydrophenazines upon excitation with 365 nm light in solvents with different polarities. Reprinted with
permission from (C. H. Lim, M. D. Ryan, B. G. McCarthy, J. C. Theriot, S. M. Sartor, N. H. Damrauer, C. B. Musgrave, G. M. Miyake, J. Am. Chem. Soc. 2017, 139,
348–355).[56] Copyright 2017 American Chemical Society.

Figure 12. O-ATRP of MMA using perylene as an organic photocatalyst and EBPA initiator in sunlight. Reproduced with permission from Ref.[51] Copyright 2014,
American Chemical Society (ACS). (Note: Further permission regarding the figure should be directed to ACS, Source: https://pubs.acs.org/doi/abs/10.1021/
ma502044 f).

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ChemistrySelect doi.org/10.1002/slct.202004194
as an irradiation source. A scope in the direction of using a
visible light source is prominent, as, in the UV range, there is a
possibility of a side reaction leading to degradation of
compounds, which may limit the scope of components used.
Ryan et al. investigated the effect of the light intensity in
the O-ATRP reaction. The nature of light controls the catalyst‘s
excited states, which eventually controls the molecular weight
distribution of the polymer. A comparative study of the
catalysts, perylene, and 3,7-di(4-biphenyl) 1-naphthalene-10-
phenoxazine was performed by changing the visible light‘s
intensities. The catalyst 3,7-di(4-biphenyl) 1-naphthalene-10-
phenoxazine was more efficient over a wide range of light
intensities.[93] Thus, for designing a reaction at low light
intensities, the demand for a robust and highly reductive
photocatalyst is deemed necessary.
6. Synopsis and Outlook
The field of O-ATRP has proved to be one of the most
successful modifications in devising a metal-free ATRP. The
range of O-ATRP can be witnessed from its employment in
synthesizing several versatile polymer structures, including the
functionalization of various polymer chain ends,[94] polymer
brush structures,[89] block,[95,96] multi-block,[97,98] and star poly-
meric structures.[99] The utilization of light enhances the control,
leads to the removal of metal catalysts, and eventually benefits
in extending this technique‘s applications. The extensive
research publications in the field during the past five years
indicate the interest in the field, which can be attributed to the
forthright and elegant nature of this particular controlled/living
polymerization technique.
The field of O-ATRP is continuously evolving with the
incorporation of novel variations to tackle the obstacles.[100]
Challenges in exposing the components of O-ATRP to a
uniform intensity of light when carried on a large scale to
produce even polymeric structure is a hurdle. Although a few
continuous flow methods[101–103] for enhancing the productivity
metal-free ATRP are ingeniously established, they have some
disadvantages, leading to the variation in the produced yield
for a scale-up difficulty in maintaining the components
exposed to the light of specified wavelength. Also, the inert
reaction conditions required for a successful O-ATRP demands
precision in establishing the suitable reaction environment
especially for a scale-up, however, the recent advancements in
performing the reaction in the oxygenated environment by
McCarthy and Miyake,[104] surely expands the scope for
innovations in the field to tackle the challenges involved.[105]
The current mechanistic understanding of O-ATRP also
demands a potential boost and emphasis, especially the
deactivation mechanism. The complete and thorough under-
standing of the mechanism is necessary and valuable for
fabricating photocatalysts with efficient structures and expand-
ing the scope of other components to a broader range.
The purpose of this review is to reveal the mechanistic
aspects and the scope of each component involved in the O-
ATRP. The field has a promising potential for magnifying the
span of controlled polymerization techniques for synthesizing
ChemistrySelect 2020, 5, 14884 – 14899
well-defined polymer structures. The recent developments in
the field involve incorporating carbon dots as
photocatalysts,[106] and progress in surface-initiated O-ATRP for
synthesizing polymer-inorganic hybrid structures[107] expand
the extent of the field beyond chemistry to a broader range of
materials science and technology. Innovative advancement like
the use of ultrasound for mediating the ATRP[108] and the recent
development of a successful light-induced ATRP in the infrared
region[109] are development fields indeed defines the prevalent
and propitious nature of ATRP for future innovations.
Acknowledgments
The authors are thankful to the All India Council for Technical
Education, New Delhi, India for financial support.
Conflict of Interest
The authors declare no conflict of interest.
Keywords: Metal-free ATRP · Photocatalysis · Photoinduced
ATRP · Polymer Chemistry · Polymerization.
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