Tricomponent Supramolecular Multiblock Copolymers with Tunable Composition via Sequential Seeded Growth

Article abstract of DOI:10.1002/anie.202105342

Synthesis of supramolecular block co-polymers (BCP) with small monomers and predictive sequence requires elegant molecular design and synthetic strategies. Herein we report the unparalleled synthesis of tri-component supramolecular BCPs with tunable microstructure by a kinetically controlled sequential seeded supramolecular polymerization of fluorescent π-conjugated monomers. Core-substituted naphthalene diimide (cNDI) derivatives with different core substitutions and appended with β-sheet forming peptide side chains provide perfect monomer design with spectral complementarity, pathway complexity and minimal structural mismatch to synthesize and characterize the multi-component BCPs. The distinct fluorescent nature of various cNDI monomers aids the spectroscopic probing of the seeded growth process and the microscopic visualization of resultant supramolecular BCPs using Structured Illumination Microscopy (SIM). Kinetically controlled sequential seeded supramolecular polymerization presented here is reminiscent of the multi-step synthesis of covalent BCPs via living chain polymerization. These findings provide a promising platform for constructing unique functional organic heterostructures for various optoelectronic and catalytic applications.

Full text of DOI:10.1002/anie.202105342

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Tricomponent Supramolecular Multiblock Copolymers with
Tunable Composition via Sequential Seeded Growth
Authors: Aritra Sarkar, Ranjan Sasmal, Angshuman Das, Akhil
Venugopal, Sarit Agasti, and Subi J. George
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202105342
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
Tricomponent Supramolecular Multiblock Copolymers with
Tunable Composition via Sequential Seeded Growth
[
a]
Aritra Sarkar, Ranjan Sasmal, Angshuman Das, Akhil Venugopal, Sarit S. Agasti*, and Subi J.
George*[a]
[
a]
Dr. A. Sarkar, R. Sasmal, A. Venugopal, Dr. S. S. Agasti, Prof. Dr. S. J. George
New Chemistry Unit (NCU) and School of Advanced Materials (SAMat)
Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR)
Jakkur, Bangalore, India-560064
E-mail: george@jncasr.ac.in; sagasti@jncasr.ac.in
Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate))
Abstract: Synthesis of supramolecular block co-polymers (BCP) with
small monomers and predictive sequence requires elegant molecular
design and synthetic strategies. Herein we report the unparalleled
synthesis of tri-component supramolecular BCPs with tunable
microstructure by
a kinetically controlled sequential seeded
supramolecular polymerization of fluorescent π-conjugated
monomers. Core-substituted naphthalene diimide (cNDI) derivatives
with different core substitutions and appended with β-sheet forming
peptide side chains provide perfect monomer design with spectral
complementarity, pathway complexity and minimal structural
mismatch to synthesize and characterize the multi-component BCPs.
The distinct fluorescent nature of various cNDI monomers aids the
spectroscopic probing of the seeded growth process and the
microscopic visualization of resultant supramolecular BCPs using
Structured Illumination Microscopy (SIM). Kinetically controlled
sequential seeded supramolecular polymerization presented here is
reminiscent of the multi-step synthesis of covalent BCPs via living
chain polymerization. These findings provide a promising platform for
constructing unique functional organic heterostructures for various
optoelectronic and catalytic applications.
Introduction
Controlled supramolecular polymerization of functional
monomers has emerged recently as an attractive bottom-up
synthetic strategy for the construction of precision organic
materials with controlled structure and composition.1 Detailed
2
mechanistic insights into the supramolecular polymerization and
3
associated pathway complexity of the process, expedited various
Figure 1. a) Molecular structures of the monomers 1, 2 and 3 used for the
synthesis of tricomponent supramolecular block co-polymers. b) Schematic
illustration of sequential seeded supramolecular polymerization process for the
synthesis of tricomponent BCP with a particular microstructure.
synthetic designs such as living seeded supramolecular
4
,5
6
polymerization, crystallization driven self-assembly and bio-
inspired reaction-driven supramolecular polymerization7 as
efficient strategies for the controlled synthesis of self-assembled
materials with low-dispersity. The next level of structural control
required would be the synthesis of multi-component
supramolecular polymers with predictive sequence and
microstructure for various applications.8 In this context,
supramolecular block-copolymerization of the complementary π-
conjugated monomers can provide functional axial organic
heterostructures with enhanced exciton migration efficiency along
Crystallization-driven self-assembly (CDSA) of kinetically
stable poly (ferrocenyldimethylsilane) (PFS)-core containing
copolymers is one of the well-established synthetic strategies for
functional supramolecular block copolymers (BCPs) with complex
sequences, topology and functions.6 However, unlike the well-
established block copolymerization reactions in its covalent
11
polymeric analogs, and CDSA approach, supramolecular block
9
the π-stacking direction, which are envisioned to have potential
applications in optoelectronics and photo-catalysis.10
copolymerization with π-conjugated small molecules directed by
specific supramolecular interaction is synthetically challenging,8
1
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RESEARCH ARTICLE
majorly due to the fast monomer exchange dynamics and lack of
characterization techniques to probe the resultant microstructure.
Thus, only recently limited but elegant synthetic attempts have
medium, to ensure a pathway complexity-driven, kinetically
controlled cooperative supramolecular polymerization process,
similar to the various protein aggregation process.2
1,22
Detailed
been made to construct supramolecular BCPs of small monomers, spectroscopic probing and visualization of the resultant BCPs
which are known to exhibit monomer exchange dynamics. This
includes thermodynamically controlled supramolecular co-
polymerization of the monomers, and sequential addition of
monomers using kinetically controlled seed induced living
supramolecular polymerization (LSP)13,14
using structured illumination microscopy (SIM)23 showed the
presence of multi-component axial heterostructures with
fluorescent emissive blocky segments.
1
2
The triblock supramolecular BCPs synthesized by Manners
group16 contain the blocky domains of the red, green and blue
dyes at the peripheral corona of the stacked polymers and thus
provides an interesting material for light-harvesting and as
fluorescent barcodes.16 In contrast to this unique example, the
multiblock fluorescent BCPs presented here, have the π-stacked
fluorophores at the backbone of the assemblies. This molecular
organization is preferred for an excitonic migration and energy
transport along the stacks which can be tapped further for
photocatalysis and various other applications in supramolecular
electronics. Thus, these supramolecular BCPs can be called as
organic heterostructures, which are reminiscent of the inorganic
heterostructures.
However,
despite
these
promising
advances,
supramolecular block co-polymerization for the synthesis of multi-
component heterostructures with more than two functional
monomers and with tunable sequence still remains to be an
important challenge to be addressed. Synthesis of tri-component
BCPs are well-established in conventional covalent polymers
using living chain polymerization by the sequential addition of
monomers.15 In a pioneering work towards this direction, Manners
and co-workers have demonstrated the extension of CSDA
strategy
to
three
different
dye-labeled
poly-
ferrocenyldimethylsilane crystallizable core
to achieve
tricomponent block copolymers with tunable sequence.16
Although, seed-induced LSP offers the possibility of sequential
addition of monomers during the supramolecular polymerization
process, lack of appropriate monomer designs with structural
similarity and independent probing features restricts the synthesis
of similar complex microstructures in supramolecular copolymers
of small dynamic monomers.8b Supramolecular block-
copolymerization strategies reported till date have used
monomers with minimal structural mismatch to avoid
Results and Discussion
Supramolecular homopolymerization of monomers 1, 2, and
3
:
Monomers 1, 2, and 3 were synthesized by multi-step synthetic
1
procedures (Scheme S1-S6) and are well-characterized by H,
13
C NMR spectroscopy, and mass spectrometry. Supramolecular
17
narcissistically self-sorted assemblies, as delicate free-energy
of interactions dictate the co-assembly of monomers.1 In this
context, it has been shown independently by our group12b,13a and
Würthner’s group13b,c that core-substituted arylene dimiides18
provide an ideal family of monomers to establish the concept of
supramolecular block-polymerization and to construct functional
nanostructures, as monomer’s functional properties can be easily
modulated by minimal structural change at their core-substitution.
Moreover, the unique spectral properties of core-substituted
arylenediimides provide an excellent tool for the spectroscopic
and microscopic characterization of the resultant heterostructures.
Thus, we have recently employed core-substituted NDIs18a for the
synthesis of supramolecular BCPs under both thermodynamic12b
and kinetic experimental conditions,13a which provide a linear
hetero-junction topology for the cNDI assemblies, compared to
the well-studied cNDI based orthogonal heterojunctions
constructed by Matile and coworkers using self-organizing
surface-initiated polymerization19 or using a zipper approach20
reaction on the surface.
homopolymerization of monomers 1-3 could be induced in
TCE/methylcyclohexane (MCH) solvent mixture of varying
composition (TCE/MCH, 10/90 (v/v) to TCE/MCH, 5/95 (v/v) for 1,
TCE/MCH, 15/85 (v/v) to TCE/MCH, 5/95 (v/v) for 2, TCE/MCH,
3c
1
0/90 (v/v) to TCE/MCH, 5/95 (v/v) for 3) and was probed
spectroscopically (Fig. S1-S4). Molecules 1, 2, and 3 forms
emissive assemblies which are evident from fluorescent and
lifetime measurements in their self-assembled state (Fig. S1c,
S2c, S3c, and S4). Emissive nature of the organized monomers
in the resultant supramolecular homopolymers (Fig. 2a) facilitated
their visualization using structured illumination microscopy (SIM),
which revealed the formation of one-dimensional fibrous
assemblies, depicted as blue (λmax = 510 nm), green (λmax = 567
nm), and red-fluorescent (λmax = 639 nm) assemblies of 1, 2 and
3
, respectively (Fig. 2b-d). The distinct absorption and emission
profiles of stacked monomers 1-3 (Fig. 2a) would aid the
independent spectroscopic probing of monomers during the
multicomponent supramolecular co-polymerization process and
the orthogonal visualization of the resultant supramolecular
copolymers using SIM microscopy (vide infra). Independent SIM
imaging showed that monomer 1 gets exclusively excited at
Channel I (λex = 488 nm, λcoll = 495-575) , monomer 2 gets excited
In this manuscript, we have elevated the complexity of
supramolecular BCP design, by reporting tri-component
supramolecular BCPs with tunable microstructure, using a
kinetically controlled, sequential seed-induced LSP process
at Channel I (λex = 488 nm, λcoll = 495-575) and Channel II (λex
61 nm, λcoll = 570-650), and monomer 3 gets excited at Channel
II (λex = 561 nm, λcoll = 570-650), and Channel III (λex = 642 nm,
coll = 655-800 nm), which would facilitate the visualization of
supramolecular co-polymers with different sequences (Fig S5-S8).
=
(
Fig.1). Three amphiphilic core-disubstituted naphthalene diimide
derivatives with ethoxy (1), ethane thiol (2) and isopropyl amine
3) core substitution, are used as the structurally similar
5
(
λ
monomers with distinct spectral properties. Further, the monomer
design also involves a tripeptide sequence containing the
diphenylalanine motif as a hydrogen-bonding motif in a nonpolar
2
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Figure 2. a) Normalized absorption and emission spectra of supramolecular homopolymers of 1 (blue), 2 (green) and 3 (red) with distinct absorption and emission
profiles ([1] = [2] = [3] = 1.5×10-5 M, TCE/MCH, 10/90 (v/v)). The emission spectra of monomer 1 (λex = 430 nm), 2 (λex = 530 nm) and 3 (λex = 600 nm). b) Time
dependent absorbance changes (monitored at 475 nm for 1, 555 nm for 2 and 360 nm for 3) of b) 1, c) 2 and d) 3, which exhibits kinetically controlled cooperative
supramolecular polymerization of the monomers. In the background of figures b-d, it shows the SIM images (inset) of the corresponding assemblies imaged through
Channel I, Channel II, and Channel III, respectively which shows the presence of blue, green and red emitting supramolecular polymers ([1] = [2] = [3] = 1.5×10-
M, TCE/MCH, 10/90 (v/v), Channel I: λex = 488 nm, λcoll = 495-575; Channel II: λex = 561 nm, λcoll = 570-650, Chanel III: λex = 642 nm, λcoll = 655-800 nm.
5
Pathway complexity of monomers 1, 2, and 3:
well with a cooperative nucleation elongation model (Fig. S13). A
decrease in lag time (tlag) with an increase in concentration for
monomers 1-3 assigned the metastable state as an on-pathway
aggregates en-route to the thermodynamically stable
supramolecular homopolymeric state.5 In an attempt to
investigate the nature of the metastable species we have
recorded absorption, emission, CD and dynamic light scattering
(DLS) spectra which indicated small ill-defined aggregates as the
metastable state, prior to the nucleation and elongation event (Fig.
S14). However, detailed molecular-level characterization of the
metastable aggregated state was hampered by its short lifetime.
The observed pathway complexity and time-dependent
nucleation-elongation growth mechanism are consistent with the
use of diphenylalanine self-assembling peptide moiety, which is
identified as one of the major components responsible for amyloid
To construct supramolecular BCPs under kinetic control, it is
important to get detailed mechanistic insights into the pathway
complexity and kinetics of supramolecular homopolymerization of
individual monomers. Hence, kinetically controlled self-assembly
of each monomer was probed by monitoring the absorbance and
CD changes at 485 nm, 555 nm, and 360 nm for 1, 2, and 3,
respectively. The addition of monomeric 1 and 3 in TCE into
TCE/MCH solvent mixture ([1] or [3] = 1.5×10-5 M, TCE/MCH,
1
0/90 (v/v)) resulted in the formation of a metastable state which
transforms into supramolecular homopolymers, via a non-linear
growth process with a lag phase (tlag of 15012 seconds and
4
765 seconds for 1 and 3, respectively) (Fig. 2b, 2d, S9, and
S10) characteristic of a cooperative mechanistic pathway. On the
other hand, monomers of 2 (TCE/MCH, 10/90 (v/v), [2] = 1.5×10-
5
21
M)
undergoes
an
instantaneous
supramolecular
fibril formation via a nucleation-elongation mechanism. The
homopolymerization. However, slow cooling (-dT/dt = 1 K/min) of
the monomers of 2 from 363 K, while probing the absorption
changes at 555 nm revealed the presence of pathway complexity
crucial role of H-bonding between the peptide moiety in driving
the self-assembly is evident from the FTIR studies in the solution
phase (Fig. S15).
(
Fig. S11a, and S11b) and monomers gets trapped in a high
energy metastable state which over time gets transformed into the
thermodynamically equilibrated homopolymeric state in
Kinetically controlled two-component supramolecular block
copolymers
a
Having established the kinetically controlled nucleation-
growth supramolecular polymerization mechanism for the
monomers 1-3, we further attempted the synthesis of
supramolecular BCPs via seeded LSP process by the sequential
addition of monomers.13 It has been shown recently that
supramolecular BCPs can be synthesized under kinetic control by
the introduction of seeds of one monomer to the metastable state
of the other monomer, to trigger a hetero-seeding event.
Following a similar strategy, we first targeted the synthesis of two-
component supramolecular BCPs with different sequences such
cooperative manner (Fig. 2c, S11c). This suggests that the
metastable state of the monomers of 2 can be accessed using
fast cooling from high temperatures. The supramolecular
polymerization kinetics of monomers 1-3, obtained by the
spectroscopic probing fits well with the Whatzkey-Finkey
autocatalytic model,2 suggesting
pathway for the assembly process (Fig. S9-S12). The presence
of a cooperative supramolecular polymerization was further
confirmed by temperature-dependent heating curves, which fits
4
a
nucleation-elongation
3
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Figure 3. Time course of supramolecular polymerization on the addition of a) 2seed into the metastable state of 1 (monitored using absorbance changes at 485 nm)
c) 3seed into the metastable state of 1 (monitored using absorbance changes at 485 nm) and e) 3seed into the metastable state of 2 (monitored using absorbance
-
5
changes at 555 nm) ([1] = [2] = [3] = 1.5×10 M, TCE/MCH, 10/90 (v/v)). The spontaneous growth of the monomers of 1 and 2, without a lag phase, hints towards
the heterogeneous seeding process. These experiments are performed for various monomer to seed ratios ([S]:[M]), which shows that the rate of growth of the
second monomer decreases with a decrease in seed concentration, reiterating the seed-induced supramolecular polymerization process. SIM images of the
synthesized two components supramolecular BCPs of b) 2seed:1monomer (0.6:1) imaged through channel I, and channel II, d) 3seed:1monomer (0.6:1) in channel I and
channel III and f) 2seed:3monomer (0.6:1) in channel II and channel III, which shows the presence of connected green-blue, red-blue and yellow-blue segments,
respectively (Channel I: λex = 488 nm, λcoll = 495–575; Channel II: λex = 561 nm, λcoll = 570–650, channel III: λex = 642 nm, λcoll = 655-800 nm).
as 2seed:1monomer, 3seed:2monomer, and 3seed:1monomer in TCE/MCH
solvent mixture (10/90 (v/v)). Seed solutions of 2 and 3 were
prepared by the sonication of respective kinetically grown
supramolecular homopolymers (10-4 M, TCE/MCH, 10/90, (v/v))
for 5 minutes (see the experimental section for details). Seed
solutions were added to the metastable states of the required
monomer and the time-dependent seeded growth was followed
by monitoring the absorbance changes of the growing monomer
obtained when 3 was used as a seed and 1 or 2 were used as
monomers (([3seed]:[1monomer] = 1:0.6, [1] = 1.5×10-5 M, and
([3seed]:[2monomer] = 1:0.6, [2] = 1.5×10-5 M,) (Fig. S17,S18).
Absorption spectra of the resultant supramolecular copolymers
show that individual aggregation characteristics of the monomers
are retained, suggesting a segmented organization of the
individual monomers (Fig S16d, S17d, S18d). All these
observations corroborate to the formation of two-component
(
485 nm for 1 and 555 nm for 2). The addition of 2seed to the
supramolecular BCPs with
3seed:2monomer composition. Further upon co-assembly, we have
2seed:1monomer, 3seed:1monomer and
metastable state of 1 ([2seed]:[1monomer] = 0.6:1, [1monomer] = 1.5×10-
5
M) triggered an instantaneous growth of the monomers of 1 with
observed a significant quenching of donor emission (either
monomer 1 or monomer 2), which hints towards an energy
transfer toward the acceptor molecules (2 or 3) with long-range
faster rate compared to the independent homopolymerization of 1
(
Fig. 3a, S16, t1/2 = 50 seconds compared to t1/2 = 386 seconds for
unseeded assembly). Further, an increase in the concentration of
seed leads to an accelerated transformation of metastable 1 to its
9
exciton migration. This further suggests the proximity between
2
the self-assembled domains of two components, probably with a
stacked organization leading to fast energy migration (Fig S16e,
S17e, S18e, S19. However, the unequivocal proof for the
assembled state, characteristic of the heterogeneous seeded
growth process (Fig. 3a, S16). 25Similar experimental results were
4
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RESEARCH ARTICLE
Figure 4. Synthesis of tricomponent supramolecular BCPs. Time course of supramolecular polymerization on sequential addition of a) 2monomer and 1 monomer to 3seed
TCE/MCH, 10/90 (v/v), [1monomer]= [2monomer] = 1.5×10- M], c) 3monomer and 1monomer to 2seed (TCE/MCH, 6/94 (v/v), [3monomer] = 2.5×10 M, [1monomer] = 1.5×10-5 M) and
5
-5
(
e) 1 monomer and 3 monomer to 2seed (TCE/MCH, 6/94 (v/v), [1monomer] = 1.5×10-5 M, [3monomer] = 2.5×10 M) to result in tricomponent supramolecular BCPs with
sequences of 3seed:2monomer:1monomer, 2seed:3monomer:1monomer and 2seed:1monomer:3monomer, respectively. SIM images of b) 3seed:2monomer:1monomer, d) 2seed:3monomer:1monomer and
f) 2seed:1monomer:3monomer tricomponent block sequences in channel I, channel II, channel III and merged channel showing presence green-red-blue, red-green-blue,
green-blue-red segments, respectively (Channel I: λex = 488 nm, λcoll = 495–575; Channel II: λex = 561 nm, λcoll = 570–650, channel III: λex = 642 nm, λcoll = 655-800
nm)
-5
supramolecular BCPs, is obtained from the detailed SIM imaging
experiments, obtained by merging the Channel I, Channel II and
Channel III (Fig. 3b, 3d, and 3f). In each supramolecular
copolymer system, a mutually exclusive probing of the various
monomeric components through different fluorescent channels
facilitated the visualization of supramolecular BCPs. Although for
a period of 24 h (Fig. S16f, S17f, and S18f). Further, time-
dependent spectroscopic and SIM microscopic probing of a mixed
seed solution of 2 and 3 homopolymers show narcissistically self-
sorted supramolecular homopolymers, which remains stable over
the period of 24 h (Fig. S23). These observations reveal the low
monomer exchange dynamics of the monomers and thus the high
kinetic stability of these assemblies. Thus, although the SIM
images portray a diffused interface between the connected
segments, we can rule out any monomer diffusion between the
blocky segments and ascribe the appearance of a diffused
interface to the limited resolution of SIM (~120 nm). Further
thermal annealing of the synthesized supramolecular BCPs
results in the formation of random supramolecular copolymers
(Fig. S24). This suggests a comparable homo- and hetero- free
energy of interaction between the monomers and hence the
segmented organization could be achieved only by
heterogeneous nucleation under kinetic control. Overall, the
studies confirm an axial heterostructure topology between
different fluorescent cNDI monomers formed by the
supramolecular block polymerization under kinetic control.
Three-component supramolecular BCPs with tunable
microstructure
supramolecular BCP between 2seed:1monomer and 3seed:2monomer
,
2
2
1
seed and 3seed have an overlapped emission with 1monomer and
monomer respectively, the selective excitation and emission of the
and 2 monomers in one of the channels successfully aided the
visualization process. Thus, supramolecular BCP of 2seed:1monomer
shows connected segments of a green-emitting domain and blue-
emitting domain with blue domain spanning over the entire fiber
(
due to overlapped emission of component 2 with component 1 in
Channel I) (Fig 3b, S20). Likewise, the two-component block co-
polymers between
3
seed:1monomer and 3seed:2monomer depicted
connected segments of red and blue-emitting domains (channel
III and channel I) and connected segments of yellow (due to
overlapped emission of component 3 and component 2 in channel
II) and green-emitting domains (channel II and channel III),
respectively (Fig 3e, 3f, S21, S22). We have further examined the
kinetic stability and monomer exchange dynamics of the
supramolecular block copolymers using time-dependent CD and
absorption changes, which show unaltered spectral features over
The successful two-component seeded supramolecular block
copolymerization of the monomers 1-3 and the resultant axial
5
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RESEARCH ARTICLE
heterostructure morphology encouraged us to explore the next
level of complexity of tricomponent supramolecular BCPs using
sequential seeded supramolecular polymerization. Hence, we
have first synthesized two-component green-red-green
supramolecular BCP by the seeded growth of 2monomer with 3seed
In conclusion, we have realized the synthesis of tricomponent
supramolecular block copolymers of cNDI π-conjugated
monomers via
a
sequential seeded supramolecular
polymerization process. Diphenylalanine appended, structurally
similar cNDI monomers with different core-substitution used in the
present study exhibited a kinetically controlled cooperative
supramolecular polymerization through an on-pathway
metastable state. Utilizing the pathway complexity exhibited by
these monomers, first, we have synthesized two-component
supramolecular BCPs with different sequences by the kinetically
controlled, seeded supramolecular polymerization process with
supramolecular homopolymers as seeds and metastable states
of 1-3 as monomer feeds. We have further used the two-
component supramolecular BCPs as the macro-seeds for the
synthesis of tri-component BCPs by the subsequent addition of
(
(
[2monomer]:[3seed] = 1:0.6, [2monomer] = 1.5×10-5 M, TCE/MCH, 10/90
v/v)) (Fig. 4a, S25a, and S25b). Next, to prepare the
tricomponent BCP, we have utilized 3seed:2monomer BCP as the
macro-seed, analogous to the macroinitiator in living radical
covalent polymerization,25 and monomers of 1 in TCE is
introduced to the 2:3 BCP solution ( [3seed]:[2monomer]:[1monomer] =
0
.6:1:1, [2monomer] = 1.5×10-5 M, TCE/MCH, 10/90) and probed the
time course of the growth of 1 using absorbance changes at 485
nm (Fig. 4a, S25c). The addition of monomer 1, in its metastable
state into the 3seed:2monomer BCP macro-seed, induces an instant
transformation of metastable 1 into the thermodynamically stable
aggregates with a faster rate (t1/2 = 36 seconds in presence of
diblock seed and t1/2 = 354 seconds in absence of seed)
different
metastable
monomers.
Thus,
tricomponent
supramolecular BCPs with different sequences could be
synthesized by varying the order of monomer addition during the
sequential seeded supramolecular polymerization process. The
distinct spectral properties of the various cNDI chromophores,
which are used as the monomers here, facilitated the in situ
selective spectroscopic probings of the heterogenous seeding
process during the sequential seeding process with different
derivatives. Further distinct blue, green, and red fluorescent
nature of the three cNDI monomers, aided the characterization of
the different microstructure of the resultant multi-component self-
assembled nanostructures with super-resolved structured
illumination microscopy imaging.
compared
polymerization of 1. This indicates that the incoming monomers of
nucleate and grow at the active ends of diblock co-polymer
leading to a tri-component supramolecular block co-polymer with
to
the
independent
nucleation-elongation
1
3
seed:2monomer:1monomer sequence. Absorption spectra of the
tricomponent co-polymer retain the individual self-assembly
characteristics of the constituent monomers, which implies the
presence of segmented domains of 1, 2, and 3 (Fig. S26). Finally,
the fluorescent nature of the cNDI facilitated visualization of the
tricomponent BCPs under SIM imaging (Fig 4b). The
tricomponent supramolecular BCP polymer was visualized by
merging channel I, channel II and channel III images, which
showed characteristics of blue-green-red-green-blue emissive
segmented topology, indicating a 3seed:2monomer:1monomer sequence
in agreement with the sequential seeding process (Fig. S27, S28,
and S29). Thermal annealing of these tricomponent
supramolecular BCPs again leads to the formation of a random
supramolecular copolymer formation (Fig. S30).
The
unprecedented
synthesis
of
tricomponent
supramolecular BCPs via sequential seeded supramolecular
polymerization demonstrated here is analogous to the use of
macroinitiators in the free-radical living polymerization synthesis
of covalent block copolymers. We envisage that the results
presented here provide a significant advancement in the
synthesis of complex supramolecular BCPs with tunable
microstructure. Further, the resultant axial heterostructure
topology with multiple organic semi-conducting monomers
provides unique opportunities for light harvesting, energy
migration and catalysis, which will be investigated in near future.
We have further investigated the possibility of synthesizing
other tricomponent sequences by changing the order of addition
of three monomers during the multi-step seeding process. Thus,
we first prepared supramolecular diblock co-polymer seeds with
2
3
seed:1monomer and 2seed:3monomer sequence by the addition of 1 and
monomers to the pre-synthesized seeds of 2 and the seeded
Acknowledgements
growth could be probed by monitoring the absorbance changes at
85 nm and 360, respectively (Fig. 4c, 4e, S31, S32). Next, to
4
We would also like to thank JNCASR and the Department of
Science and Technology, Government of India, for financial
support. In addition, the funding from Sheikh Saqr Laboratory
synthesize tricomponent supramolecular BCP of different
sequences, we have introduced monomers of 1 to 2seed:3monomer
diblock co-polymer seeds and monomers of 3 to 2seed:1monomer
diblock co-polymer seeds (Fig. 4c, e, S31c, S32c). Spectroscopic
probing revealed the formation of tricomponent supramolecular
BCPs with respect to faster kinetics of growth of the added
monomers (Fig. S31, S32). SIM imaging proved the presence of
tri-component supramolecular BCPs with characteristics of blue-
red-green-red-blue and blue-red-green-red-blue emissive
segmented topology is consistent with the expected
(
SSL), JNCASR is also acknowledged. S. J. G. acknowledges the
funding received from SwarnaJayanti Fellowship Award
DST/SJF/CSA01/2016-2017) and Department of Biotechnology,
(
Government of India, for the Indo-Switzerland Joint Research
project (BT/IN/Swiss/55/SJG/2018-2019). AS and RS thanks
CSIR for fellowship.
Keywords: supramolecular polymers • supramolecular block
copolymers • self-assembly • seeded growth • peptide
2
seed:3monomer:1monomer and 2seed:1monomer:3monomer sequence (Fig. 4d,
f, S33-S37 ).
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Entry for the Table of Contents
Synthesis of tricomponent supramolecular block copolymers with tunable microstructure is demonstrated by a kinetically controlled
sequential seeded supramolecular polymerization fluorescent core-substituted naphthalenediimide derivatives.
Institute and/or researcher Twitter usernames: @georgelabJNCASR
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