Seeded Supramolecular Polymerization in a Three-Domain Self-Assembly of an N-Annulated Perylenetetracarboxamide

Article abstract of DOI:10.1002/chem.201602344

The three-domain cooperative supramolecular polymerization of 1, together with the lag time in which the monomeric species remains inactive, allows seeded supramolecular polymerization to be performed. The kinetic experiments demonstrate that only seeds based on the intermediate aggregate are able to propagate the supramolecular polymerization of 1 from their active sites. The results presented herein constitute a new example of kinetically controlled supramolecular systems and contribute to expanding knowledge about the structural requirements of a self-assembling molecule to experience seeded supramolecular polymerization.

Full text of DOI:10.1002/chem.201602344

DOI: 10.1002/chem.201602344
Full Paper
&
Cooperative Effects
Seeded Supramolecular Polymerization in a Three-Domain Self-
Assembly of an N-Annulated Perylenetetracarboxamide
Elisa E. Greciano and Luis Sꢀnchez*[a]
Abstract: The three-domain cooperative supramolecular
polymerization of 1, together with the lag time in which the
monomeric species remains inactive, allows seeded supra-
molecular polymerization to be performed. The kinetic ex-
periments demonstrate that only seeds based on the inter-
mediate aggregate are able to propagate the supramolec-
ular polymerization of 1 from their active sites. The results
presented herein constitute a new example of kinetically
controlled supramolecular systems and contribute to ex-
panding knowledge about the structural requirements of
a self-assembling molecule to experience seeded supra-
molecular polymerization.
Introduction
form the corresponding supramolecular polymers by itself. The
coassembly of both monomers generates an active dimer that
grows rapidly to form a supramolecular polymer.[7] The sponta-
neous polymerization of a bowl-shaped corannulene derivative
containing five amide groups exemplify the concept of LSP.[8]
Closely related with this idea are examples in which temporally
inactive species can evolve to yield supramolecular polymeri-
zation in different ways: 1) by following two different elonga-
tion pathways in equilibrium (EQ) that provide aggregated sys-
tems with different properties (helicity or light absorption), or
2) by ensuring supramolecular polymerization is inactive until
a specific seed is added. Competing pathways in the self-as-
sembly of S-chiral oligo(p-phenylenevinylene), which yields the
two opposite helical structures;[6] the temporal evolution of J
aggregates formed by porphyrin-based self-assembling mole-
cules;[9] and different emissive aggregated states generated in
the self-assembly of a platinum(II) complex[10] exemplify the
first strategy. In the second strategy, for kinetically trapped
species to evolve, the monomeric species can be kinetically
trapped in an inactive state by the presence of an additional
noncovalent interaction that generates an aggregation-incom-
petent conformation. The addition of a seed initiates rapid
supramolecular polymerization. This is the case for the acceler-
ated self-assembly of a series of perylene bisimide (PDI)
organogelators.[11]
In good correlation with the general polymerization strategy of
a repetitive sequence of monomeric units to generate the
polymeric chain, Lehn and co-workers reported the first exam-
ple of a supramolecular polymer formed by hydrogen-bonding
interactions between uracil and 2,6-diaminopyridines deriva-
tives.[1] From this first example, to date, great advances have
been achieved in the area of supramolecular polymerization
both from basic and practical points of view.[2] The function of
a supramolecular polymer is directly related to the mechanism
followed by the monomeric units to form the polymeric chain.
Thus, two extreme supramolecular polymerization mecha-
nisms, isodesmic or nucleation–elongation, have been de-
scribed and amply investigated.[3] However, to emulate natural
or man-made polymerization processes, such as actin polymer-
ization or seeded living polymerization, respectively,[4,5] far-
from-equilibrium systems have been recently reported.[6] The
possibility of attaining kinetically controlled supramolecular
polymers, together with the similarity of initiation–propagation
in living polymerization and nucleation–elongation in a cooper-
ative supramolecular polymerization, have inspired very few re-
ports on the new concept of supramolecular polymerization
known as living supramolecular polymerization (LSP), which
yields supramolecular polymers with controlled length and
narrow polydispersity.[7]
The abovementioned examples share three common fea-
tures that allow valuable information to be extracted to define
the requisites for a kinetically trapped self-assembling system
to yield accelerated supramolecular polymerization: 1) aggre-
gation proceeds through a cooperative mechanism; 2) the nu-
cleation regimen is retarded, which allows kinetic control of
the process; and 3) it is possible to prepare the seeds in a sepa-
rate manner that can be further act as initiators. In addition,
from a chemical structure point of view, a number of the re-
ported examples of seeded supramolecular polymerization
(SSP) also share the presence of a 3,4,5-trialkoxy-N-(alkoxy)ben-
zamide moiety capable of forming different supramolecular
LSP consists of cooperative supramolecular polymerization
in which the spontaneous self-assembly of monomeric units,
joined together by intramolecular noncovalent forces, is
strongly accelerated by the addition of an initiator unable to
[a] E. E. Greciano, Prof. Dr. L. Sꢀnchez
Departamento de Quꢁmica Orgꢀnica I Facultad de Ciencias Quꢁmicas
Universidad Complutense de Madrid
Ciudad Universitaria s/n; 28040 Madrid (Spain)
E-mail: lusamar@quim.ucm.es
Supporting information for this article can be found under http://
dx.doi.org/10.1002/chem.201602344.
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Figure 1. a) Chemical structure of the N-annulated perylenetetracarboxamide 1. b) Photograph of the organogels formed by 1 in methylcyclohexane (MCH)
and toluene (Tol). AFM height images of 1 on highly oriented pyrolytic graphite (HOPG) as a substrate in MCH (c) and Tol (d) as solvents (298 K, 1ꢂ10À5 m;
z scale=35 (c) and 25 nm (d)). The insets in c) and d) show the height profiles along the white lines. e) Temperature-dependent UV/Vis spectra of 1 in MCH/
Tol 70/30 (1ꢂ10À5 m, from 363 to 293 K). The black lines depict the UV/Vis spectra of 1 at 20, 52, and 908C. f) Plot of the variation of the degree of aggrega-
tion of 1 versus temperature at cT =1ꢂ10À5 m and in different mixtures of MCH/Tol.
structures through the formation of intra- or intermolecular hy-
drogen-bonding interactions.[9,11]
supramolecular polymerization, which is diagnostic of SSP, is
higher than that in the latter case. The results presented
herein expand our comprehension of the mechanistic and
structural details of supramolecular polymers to provide a gen-
eral route to advanced, functional, aggregated structures.
To increase our knowledge on the structural rules that a rela-
tively simple self-assembling unit should fulfil to experience an
efficient SSP process, herein we report on the seeded self-as-
sembly of an N-annulated perylene endowed with two amide
functional groups in each of its peripheral side chains (1; Fig-
ure 1a). Similarly to the PDIs and porphyrins that have been re- Results and discussion
ported to experience a seeded process, compound 1 is deco-
Synthesis and supramolecular polymerization mechanism
rated with a 3,4,5-trialkoxy-N-(alkoxy)benzamide moiety; supra-
molecular polymerization in Tol is cooperative with a thermal
hysteresis. These features make it possible to kinetically trap
the monomeric species. Interestingly, the addition of a more
apolar solvent, such as MCH, provokes a unique three-step co-
operative supramolecular polymerization process. We have de-
tected three different species by UV/Vis: the monomeric unit
(M), an intermediate aggregated species (I), and the completely
aggregated state (A). We have evaluated SSP experienced by
1 at different concentrations and upon adding different seeds,
corresponding to I and A. In the former case, acceleration of
Compound 1 was obtained in a similar multistep protocol to
that previously reported by our research group to prepare N-
annulated perylenedicarboxamides (see Scheme S1 in the Sup-
porting Information).[12] NMR and FTIR spectroscopic data, as
well as the corresponding high-resolution mass spectra, con-
firm the proposed chemical structure (see the Supporting In-
formation).
A first indication of the tendency of 1 to self-assemble in so-
lution through hydrogen-bonding interactions between the
amides and p stacking of the aromatic unit is inferred by pre-
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liminary concentration-dependent 1H NMR spectroscopy ex-
periments in CDCl3. In good correlation with some other exam-
ples,[13] increasing the concentration results in a downfield shift
of both resonances at dꢀ7.6 and 7.4 ppm, corresponding to
the inner and outer amides, respectively, and in a shielding
effect on the protons corresponding to the aromatic core, es-
pecially those at dꢀ8.6 ppm, which are ascribable to protons
of the bay position of the perylene unit (Figure S1 in the Sup-
porting Information). This trend of 1 to self-assemble in more
apolar solvents, such as MCH and Tol, has been also studied by
dynamic light scattering (DLS). The correlation functions ob-
tained for 1 in MCH exhibit a sum of exponential decays to-
gether with an oscillatory term. This behavior has been previ-
ously described for highly absorbing macromolecules or aggre-
gated species and it has been rationalized by the presence of
different species in convective motion.[14] The average hydrody-
namic radii obtained by analyzing the correlation functions ob-
tained for 1 in MCH is 296 nm (Figure S2a in the Supporting In-
formation). However, CONTIN analysis of the correlation func-
tions of 1 in Tol shows a very broad distribution of particle
sizes indicative of the presence of species with very different
morphologies (Figure S2b in the Supporting Information).
Compound 1 readily form gels in apolar solvents, such as
MCH or Tol, which implies the formation of organized supra-
molecular structures (Figure 1b). The solvent strongly condi-
tions the morphology of the aggregates visualized by AFM of
dilute solutions of 1 (1ꢂ10À5 m). In more apolar MCH, bundles
of fibers constitutive of the organogel are clearly visible. The
diameter of the thinner fibers is around 7 nm (Figure 1c and
Figure S3 in the Supporting Information). However, the AFM
images of 1 in Tol reveal the formation of nanoparticles to-
gether with isolated fibrillar structures (Figure 1d). The dissimi-
lar morphologies observed in MCH or Tol have also been re-
ported for PDI organogelators capable of undergoing SSP.[11b]
Variable-temperature UV/Vis (VT-UV/Vis) experiments, in dif-
ferent solvent at different concentrations, have been utilized
to achieve a detailed investigation of the supramolecular poly-
merization mechanism. In analogy with that reported for the
aggregated state of a comparable N-annulated perylenedicar-
boxamide,[12a] compound 1 in an aggregated state features
a broad band centered at l=423 nm that splits upon heating
into three bands at l=398, 427, and 452 nm (Figure 1e). The
strong trend of 1 to self-assemble in an apolar solvent such as
MCH and at a total concentration (cT) as low as 5ꢂ10À6 m im-
pedes the observation of the abovementioned spectroscopic
features of 1 in a molecularly dissolved state. Consequently,
the addition of a more polar cosolvent, such as Tol, is necessa-
ry to obtain the molecularly dissolved state for 1. The corre-
sponding cooling curves of 1 in mixtures of MCH/Tol show
nonsigmoidal curves with very high elongation temperatures
(Te), that is, the temperature at which the nucleation regimen
changes to the elongation one,[3] which is indicative of cooper-
ative supramolecular polymerization. Closer inspection of the
cooling curves shows a subtle transition at intermediate tem-
peratures (Figure S4 in the Supporting Information). The transi-
tion between the nucleation and elongation regimens cannot
be observed because of the strong trend of 1 to aggregate.
However, a clear intermediate transition is observed at around
508C in the heating curves. Interestingly, increasing the per-
centage of Tol allows two defined transitions at around 80 and
508C to be unambiguously observed; these are diagnostic of
a three-step supramolecular polymerization (Figure 1 f and Fig-
ure S5 in the Supporting Information). The heating curves of
1 involve the contribution of three different species, namely,
the monomeric unit M; annealed, aggregated intermediate
species I; and completely aggregated state A. The UV/Vis spec-
tra at 20, 52, and 908C show different crossing points that are
indicative of the formation of three different chemical species
(Figure 1 f). Notably, the elongation temperatures observed in
the heating (Te) and cooling (Te’) processes, even if very high,
are not identical; thus indicating thermal hysteresis. This be-
havior has been identified in comparable PDIs as a fingerprint
of a kinetically controlled supramolecular polymerization in
which an inactive monomeric species is present.[11]
The Te and Te’ values decrease notably with Tol as the solvent
in the corresponding heating and cooling curves (Figure 2a).
The increasing difference between these two transition tem-
peratures indicates that the supramolecular polymerization of
1 can be kinetically controlled in this solvent. The VT-UV/Vis ex-
periments performed in Tol show that the spectrum at 208C
exhibits the same shape as that observed for 1 at intermediate
temperatures (ꢀ508C) in mixtures of MCH/Tol (Figure 2b).
These studies suggest that in the aggregation process of 1 in
Tol only the denaturation and annealing steps occur involving
the monomeric unit M and the annealed, aggregated inter-
mediate species I.
The nonsigmoidal transitions observed for the denaturation–
annealing processes in both Tol and mixtures of MCH/Tol can
be fitted to the EQ model to extract the corresponding ther-
modynamic parameters of the self-assembly process, namely,
the enthalpy of elongation, DHe; the entropy of elongation,
DS; and the nucleation penalty, DHn (Table 1 and Figure S6 in
the Supporting Information).[15] Considering the differences in
polarity of the solvent and concentration of the sample, the
values of the thermodynamic parameters are similar.
Data extracted from the VT-UV/Vis experiments of 1 show
good agreement with that reported for the kinetically con-
trolled supramolecular polymerization of PDIs[11] with a striking
difference in the three-step aggregation process. The forma-
tion of up to nine-membered pseudocycles through intramo-
lecular hydrogen-bonding interactions between bis-amides or
bis-ureas has been utilized to justify the origin of the inactiva-
tion of the monomers in the case of PDIs.[16] Thus, the forma-
tion of an intramolecular hydrogen-bonding interaction be-
tween the NÀH of the amide functional group and one of the
Table 1. Thermodynamic parameters of the supramolecular polymeri-
zation of 1 derived from the EQ model.
1
Tol (1ꢂ10À4 m)
MCH/Tol (70/30; 1ꢂ10À5 m)
DHe [kJmolÀ1
]
À109.7Æ3.5
À258Æ11
À103.1Æ3.1
À198Æ9
DS [JKÀ1 molÀ1
]
DHn [kJmolÀ1
]
À15.1Æ0.8
À18.0Æ0.9
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protons upon increasing the temperature (Figure S7b
in the Supporting Information). The shift of both res-
onances can be reasonably assigned to the intramo-
lecular hydrogen-bonding interaction between the
NÀH of the inner amide and the carbonyl of the
outer amide and also to the intramolecular hydro-
gen-bonding interaction between the NÀH of the
outer amide and the carbonyl of the inner amide
(Figure 3a). Definitive evidence of the formation of
the seven-membered pseudocycles involving the two
amide groups has been obtained by a 2D-ROESY ex-
periment (Figure 3b). This experiment shows
through-space intramolecular contacts between the
ortho proton of the benzamide unit with the NÀH of
the outer amide, with the proton of the external
3,4,5-trialkoxybenzamide moiety, and also with the
methylene joint to the oxygen in this same unit
(arrows in Figure 3a and circles in Figure 3b). These
through-space contacts can only be explained by the
formation of intramolecular hydrogen-bonded rings.
Notably, these kinetically inactivated monomeric
rings still have additional NÀH and carbonyl groups
that, under the appropriate conditions of concentra-
tion and/or temperature, can readily grow up to form
a supramolecular polymer (Figure 3c). These inter-
mediate species, I, in which the four amides partici-
pate in two intramolecular and two intermolecular
hydrogen-bonding interactions, feature the UV/Vis
spectrum observed at temperatures of around 508C
in mixtures of MCH/Tol and the spectrum at room
temperature in pure Tol with an absorption maxi-
mum at l=430 nm and two shoulders at l=410
and 456 nm (Figures 1c and 2b). The rearrangement
of the two intramolecular hydrogen bonds into inter-
molecular hydrogen bonds induces stretching of the
ethylene spacer, which allows the formation of a hy-
drogen-bonding array between the four amides and
optimizes p stacking of the N-annulated perylene
(Figure 3c).[18] As a consequence, the UV/Vis spec-
trum of the completely aggregated species A of 1,
observed at low temperatures in mixtures of MCH/
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Figure 2. a) Heating ( ) and cooling ( ) curves of 1 at different concentrations in Tol
(cT =1.5ꢂ10À4, 1.0ꢂ10À4, and 0.9ꢂ10À4 m). b) VT-UV/Vis spectra of 1 in Tol (1ꢂ10À4 m).
carbonyls of the imide moiety produces a seven-membered
pseudocycle that cannot elongate to form the supramolecular
polymer. However, compound 1 is endowed with two amide
functional groups attached to an ethylene spacer. The structur-
al features of 1 are appropriate to form two different seven-
membered pseudocycles involving the two amide groups (Fig-
ure 3a). The synergy of UV/Vis, variable-temperature (VT)
1H NMR, and 2D-ROESY spectroscopy experiments in chloro-
form at cT =2ꢂ10À3 m has been utilized to demonstrate the
formation of the inactivated monomer of 1.[17] Under these
conditions of concentration and solvent, the UV/Vis spectrum
of 1 exhibits the characteristic pattern of the monomeric spe-
cies M with three absorption maxima at l=398, 427, and
452 nm (Figure S7a in the Supporting Information).
Tol, exhibits a broad absorption maximum at l=423 nm (Fig-
ure 1c). This spectrum coincides exactly with that previously
reported by our research group for the aggregated species of
an N-annulated perylenedicarboxamide organogelator.[12a] The
conversion of the kinetically inactivated monomers M into the
intermediate supramolecular polymers I, and the further con-
version of these intermediate aggregates into the final supra-
molecular polymer A can reasonably justify the three-step
supramolecular polymerization process observed in the corre-
sponding heating curves of 1 in mixtures of MCH/Tol.
Time-dependent SSP
The cooperative supramolecular polymerization of 1, the hyste-
resis loop observed in the Te and Te’ values, and the possibility
of forming inactivated monomeric species imply the possibility
The VT-1H NMR spectra of 1 at 2ꢂ10À3 m show a slight
shielding effect on both triplets corresponding to the amide
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Figure 3. a) Chemical structure of the inactivated monomeric species of 1 showing the two possible intramolecular hydrogen-bonded rings. b) 2D-ROESY
NMR spectrum (CDCl3, 300 MHz, 8 mm, 298 K) of 1. The circles highlight the intermolecular through-space coupling signals between the protons of the hydro-
gen-bonded rings indicated by the curved arrows in a). c) Schematic representation of the proposed three-step equilibria that yield the supramolecular poly-
merization of 1.
of far-from-EQ processes and, consequently, the possibility of
investigating the operation of SSP. The difference between the
Te and Te’ values, which increase with decreasing cT, facilitates
an effective temperature range to maintain inactivated mono-
meric species of 1 (Figure S8 in the Supporting Information). In
this range of temperatures, the formation of the kinetically
trapped monomeric species is preferred over supramolecular
polymerization. However, the thermodynamically more stable
supramolecular polymers of 1 should induce the transforma-
tion of monomeric hydrogen-bonded rings M into intermedi-
ate I or completely aggregated A over time. The spectroscopic
differences found between the M, I, and A species can be uti-
lized for identification to follow the kinetic evolution of the
supramolecular polymerization of 1 by monitoring different pa-
rameters, such as concentration or temperature (Figure 4a and
b). All time-dependent experiments were performed through
the rapid heating of a sample to 908C, followed by fast cooling
(25 KminÀ1) to the corresponding temperature. The time-de-
pendent experiment was launched 1 min after reaching this
temperature. Due to the very high values of Te found in the
mixtures of MCH/Tol, we performed the time-dependent ex-
periments by using Tol as the solvent.
tively high concentration (4ꢂ10À5 m), the kinetic profile shows
two transitions. The first one can be ascribable to the very
rapid conversion of the kinetically trapped monomers into the
intermediate aggregates I (Figure 4a). The second transition
yields the completely aggregated species A, as demonstrated
by the absorption spectrum, which exhibits a broad band cen-
tered at l=423 nm (Figure S9a in the Supporting Information).
Upon decreasing the concentration to 1ꢂ10À5 m, the kinetic
profile shows a single transition with a clear sigmoidal shape
that is diagnostic of an autocatalytic process in which the nu-
cleation and elongation regimens are involved, but separated
by a lag time of around 10 min (Figure 4a).[8,11] At this concen-
tration, the UV/Vis spectrum of the final species corresponds
to the intermediate aggregate I with an absorption maximum
at l=430 nm and two shoulders at l=410 and 456 nm (Fig-
ure S9b in the Supporting Information). These kinetic experi-
ments demonstrate that, upon increasing the concentration of
1 in Tol, it is possible to reach the completely aggregated spe-
cies with four intermolecular hydrogen bonds between the
amides, which were only observed previously in mixtures of
MCH/Tol.
Considering the hysteresis loop observed between the Te
and Te’ values, we also evaluated the kinetic evolution of the
transformation of the monomeric species by changing the
We first evaluated the effect of concentration on the kinetic
evolution of the supramolecular polymerization of 1. At a rela-
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Figure 4. Kinetic profiles of aggregate formation in Tol a) at different concentrations (258C, 4ꢂ10À5 m and 1ꢂ10À5 m), and b) at different temperatures at a con-
centration of 1ꢂ10À5 m. c) Kinetic profiles of the SSP of 1 by adding different seeding species at 298C.
temperature. Increasing the temperature results in kinetically
retarded nucleation, in which the intramolecularly hydrogen-
bonded monomeric rings are trapped longer; up to 40 min at
298C (Figure 4b). In all cases, the sigmoidal shape of the kinet-
ic profiles indicates an autocatalytic nucleation–elongation pro-
cess that can be utilized to perform SSP. Unlike the previous
examples of SSP,[8,11] compound 1 can form two different ag-
gregates (I and A) with perfectly defined spectroscopic fea-
tures. Therefore, we have prepared two different seeds to ini-
tiate acceleration of the supramolecular polymerization of 1.
Following a similar strategy to that described for PDIs,[11] we
prepared both seeds of I and A species by sonicating a 1ꢂ
10À5 m solution of 1 in MCH/Tol (70/30) for different time inter-
vals, and following the absorption spectra as a fingerprint of
the nature of the seed.
same as that achieved for the addition of the mixture MCH/Tol
(70:30; 10 mL; Figure 4c). These data indicate that completely
aggregated A species does not possess active sites to propa-
gate the supramolecular polymerization of 1, which, under
these conditions, is only accelerated by the presence of the
less polar solvent MCH.
Conclusion
The supramolecular polymerization of N-annulated perylene-
tetracarboxamide 1 has been thoroughly investigated by using
different conditions of concentration and solvent. The studies
presented herein contribute to increasing knowledge of the
structural requirements necessary for a self-assembling unit to
experience far-from-EQ aggregation. Compound 1, which read-
ily forms organogels in apolar solvents, self-assembles cooper-
atively into fibrillar supramolecular structures in MCH or into
nanoparticles together with isolated fibrillar structures in Tol.
This cooperative supramolecular polymerization of 1 is strongly
conditioned by the solvent and heating/cooling cycles. Thus,
a three-step supramolecular polymerization process is ob-
served for 1 in a mixture of MCH/Tol, which indicates the for-
mation of two different aggregated species, I and A, that show
perfectly distinguishable absorption features. VT-UV/Vis experi-
ments in Tol show that the cooperative supramolecular poly-
merization of 1 yields the partially aggregated species I and
also a hysteresis loop in the elongation temperatures. This hys-
teresis loop allows kinetic studies to be developed to control
the supramolecular polymerization of 1 through the inactiva-
tion of the monomeric species. UV/Vis, VT-1H NMR, and 2D-
ROESY experiments at cT =2ꢂ10À3 m in chloroform have been
utilized to demonstrate the formation of intramolecular hydro-
gen bonds between the amide functional groups to generate
the inactivated monomer species of 1. Time-dependent experi-
ments demonstrate the evolution of these monomeric species
into aggregates. At relatively high concentrations (4ꢂ10À5 m),
the kinetic profile shows the rapid conversion of monomeric
species into fully aggregated supramolecular structures. At
a lower concentration (1ꢂ10À5 m), the monomeric species re-
mains inactive for a time ranging from 10 to 40 min, depend-
ing on the temperature, yielding intermediate aggregates I.
This lag time has been harnessed to perform SSP by using dif-
Taking into account the experimental data extracted from
the time-dependent supramolecular polymerization experi-
ments, seeded polymerization was performed at a concentra-
tion of 1ꢂ10À5 m in Tol at 298C (Figure 4c). We first evaluated
the ability of the seed corresponding to the intermediate ag-
gregate to accelerate the supramolecular polymerization of 1.
Thus, the addition of the seed (10 mL) prepared by sonicating
a 1ꢂ10À5 m solution of 1 in a mixture of MCH/Tol (70:30) for
10 min (Figure S10 in the Supporting Information), to achieve
partially aggregated species I, into a freshly prepared mono-
meric solution of 1 (1ꢂ10À5 m in Tol, heated to 908C and rapid-
ly cooled to 298C) reduced the lag time from 40 to 10 min
(Figure 4c). This lag time is reduced or totally cancelled out by
adding increasing amounts of the seeding sample (Figure S10
in the Supporting Information). The acceleration of the supra-
molecular polymerization of 1 has also been evaluated by
adding the same amount (10 mL) of the mixture of MCH/Tol
(70:30). In this case, the lag time is slightly reduced from 40 to
20 min, which implies that the supramolecular polymers of
1 can be propagated from the active sites of the intermediate
aggregated seed. Finally, we also evaluated the capability of
the seed corresponding to the fully aggregated species A of 1,
obtained by sonicating a 1ꢂ10À5 m solution of 1 in a mixture
of MCH/Tol (70:30) for only 1 min, to accelerate the supra-
molecular polymerization of 1 (Figure S11 in the Supporting In-
formation). In this case, after the addition of this seed of A spe-
cies (10 mL), the lag time of the kinetic process is exactly the
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banne, J. M. Mitchels, R. M. Richardson, M. A. Winnik, I. Manners, Nat.
Chem. 2010, 2, 566–570.
ferent seeds. The kinetic experiments demonstrate that only
seeds based on intermediate aggregate I are able to propagate
the supramolecular polymerization of 1 from the active sites.
The results presented herein expand our knowledge of the
structural requirements necessary for a self-assembling mole-
cule to experience LSP to enhance and/or modulate the physi-
cal, chemical and/or optical properties of the final supramolec-
ular structures. Work is currently in progress in our research
group to further elucidate both experimentally and theoretical-
ly the nature of the inactivated monomeric species, as well as
on three-step supramolecular polymerization involving three
different monomeric, partially aggregated, and completely ag-
gregated species.
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This work was supported by the MINECO of Spain (CTQ2014-
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Keywords: cooperative effects · kinetics · polymers · self-
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Received: May 17, 2016
Published online on && &&, 0000
Chem. Eur. J. 2016, 22, 1 – 8
www.chemeurj.org
7
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
FULL PAPER
Controlled coming together: The coop-
erative supramolecular polymerization
of an N-annulated perylene endowed
with two amide functional groups is in-
vestigated by changing the conditions
of self-assembly. Control of the lag time
in which the monomeric species remain
inactive allows seeded supramolecular
polymerization to be performed and
studied with different seeding species
(see figure).
&
Cooperative Effects
E. E. Greciano, L. Sꢀnchez*
&& – &&
Seeded Supramolecular
Polymerization in a Three-Domain
Self-Assembly of an N-Annulated
Perylenetetracarboxamide
&
&
Chem. Eur. J. 2016, 22, 1 – 8
www.chemeurj.org
8
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!