Hydrogen bonding-assisted loosely packed crystals of a diaminomaleonitrile-modified tetraphenylethene compound and their photo- and mechano-responsive properties

Article abstract of DOI:10.1039/c7tc03404k

In this study, loosely packed crystals with the building blocks of aggregation induced emission (AIE)-active TPE-MN molecules were constructed with the assistance of intermolecular hydrogen bonding. The AIE properties of the compound TPE-MN were studied.

Full text of DOI:10.1039/c7tc03404k

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Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
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Jo uP rl ne aa sl eo fd oM na ot et r ai ad l jsu sCt hme am r gi si nt rs y C
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DOI: 10.1039/C7TC03404K
Journal Name
ARTICLE
Hydrogen-Bonding Assisted Loosely Packing Crystals of a
Diaminomaleonitrile-modified Tetraphenylethene Compound and
their Photo- and Mechano-Responsive Properties
Received 00th January 20xx,
Accepted 00th January 20xx
Qiuyi Huang, Tao Yu,a,† Zongliang Xie, Wenlang Li, Leyu Wang, Siwei Liu, Yi Zhang, Zhenguo
a,†
a
a
a
a
a ,*
DOI: 10.1039/x0xx00000x
a,*
a
b
Chi, Jiarui Xu, Matthew. P. Aldred
www.rsc.org/
In this study, loosely packing crystals with the building blocks of AIE active TPE-MN molecules were constructed with the
assistance of intermolecular hydrogen bonding. Aggregation induced emission (AIE) properties of the compound TPE-MN
were studied. From single crystal analyses, sandwich-like crystal structure with tightly packing areas (TPE moieties) and
loosely packing areas were observed. Nevertheless, TPE-MN crystals display non-emissive properties in the loosely packing
crystalline state. Differential scanning calorimetry (DSC) studies, powder X-ray diffraction analyses and various
photophysical studies further reveal that the loosely packing crystal structure can provide enough space for significant
molecular rotations and vibrations to occur, which leads to the emission quenching. By breaking the loosely packing crystal
structure with mechanical force or UV irradiation, the emission band with the maximum at ca. 562 nm can be turned on.
These results can serve as a basis for constructing multi-responsive materials with turn-on emissive properties.
Introduction
packing crystals with drastic color and/or photophysical
property changes.
The well-established concept of AIE was first reported by
Molecules in the crystalline state are stacked regularly and
usually display more rigid packing modes than in amorphous
Tang in 2001.[7] By restriction of intramolecular vibrations and
rotations, AIE compounds become much more emissive after
[1]
states. Many efforts have been tried to construct crystalline
materials in the loosely packing mode for their widespread
applications in gas storage, gas separation, catalysis and
[8]
“
aggregation”. With the drastic emission enhancement in the
aggregate state, compared to the dilute solution-state, these
compounds show immense potential in many applications,
[
2]
sensing. To avoid a tightly parking mode, different types of
intermolecular interactions have been used to decrease the
energy of the loosely packing crystals. Many loosely packing
crystalline material systems, especially porous organic
crystalline materials including zeolites,[3] metal-organic
[9]
especially in sensing and as mechanical responsive materials.
The restriction of the intramolecular rotations and vibrations
of AIE-active materials in the aggregate state switches the
fluorescence decay processes of the excited molecules from
non-emissive to emissive. The majority of the reported AIE
processes have been in a solution medium, which prevents the
applications of AIE-active materials as responsive materials. If
the rotational and vibrational restriction processes of AIE
molecules can be realized in the solid-state, then the
applications of AIE-active materials will become more useful in
sensing and in mechano-responsive related fields. In previous
studies several strategies have been reported for the
[
4]
[5]
frameworks (MOFs), covalent organic frameworks (COFs)
and hydrogen-bonding organic frameworks (HOFs),[ have
aroused great attention. Compared with other types of loosely
packing crystals, loosely packing crystals with intermolecular
hydrogen bonding have outstanding features, such as solvent-
6]
process ability, facile regeneration by recrystallization and self-
repairing capabilities.[
6h-6i]
Constructed by weak noncovalent
intermolecular interactions, these crystals may be sensitive to
the external environment and to stimuli. Thus, it is possible to
tune the crystal structure and the packing mode for the loosely
production
materials.
of
high-contrast
mechano-responsive
[9,10]
For example, Tian and co-workers discovered
that acridonyl-tetraphenylethene exhibits an intriguing turn-on
luminescence by tuning the molecular conformation with
mechanical stimuli.[
10a]
In addition, high-contrast mechano-
a
PCFM Lab, GDHPPC Lab, Guangdong Engineering Technology Research Center for responsive properties were also achieved by breaking the
High-performance Organic and Polymer Photoelectric Functional Films, State Key
Laboratory of OEMT, School of Chemistry, Sun Yat-sen University, Guangzhou
intermolecular interactions
(π-π stacking, intermolecular
hydrogen bonding and others), which could quench the
emission bands, with mechanical stimuli.[10b-10e] However, high-
contrast mechano-responsive materials are still rare and new
strategies are quite urgent. As mentioned above, materials
5
10275 (China). *E-mail: ceszy@mail.sysu.edu.cn; chizhg@mail.sysu.edu.cn.
Durham University, Durham DH1 3LE, UK.
Dr. Q. Huang and Dr. T. Yu contributed equally to this work.
b
†
Electronic Supplementary Information (ESI) available: [Synthetic procedures,
experimental details and supplemental figures.]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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that exhibit hydrogen bonding assisted loosely packing crystal
structures could allow
View Article Online
DOI: 10.1039/C7TC03404K
Figure 1. Synthetic route for compound TPE-MN.
enough space for significant intramolecular rotations and Figure 2. (a) Electronic absorption spectrum of TPE-MN in
-5
vibrations to occur even in the solid-state. In addition, the dichloromethane solution, concentration = 1.0×10 mol/L, (b)
weak and sensitive structures which is attributed to the weak Emission spectra of TPE-MN in THF/water solvent mixtures
intermolecular interactions might bring about the restriction
process with turn-on emission properties after external
mechano- or irradiative-simulations. Therefore, designing AIE-
active molecules with loosely packing crystal structures in the
solid-state could become an appealing strategy for designing
responsive materials.
containing different water fractions (from 0% to 90%),
concentration = 1.0×10 mol/L and excitation at 365 nm. The
inset picture shows photographs of TPE-MN in THF solution
-5
(left) and THF/water (90% water fraction) (right).
The emission band of TPE-MN in pure THF is weak, which is
due to the excessive intramolecular rotations in the dilute
solution-state, and perhaps some contribution from the
solvent polarity.[8] However, the emission intensity is enhanced
considerably at 90% v/v water fraction with an emission peak
located at ca. 530 nm. This dramatic enhancement of emission
intensity indicates the formation of aggregate particles due to
the poor solubility of TPE-MN in the mixed solvent system with
high water content and the subsequent restriction of the
Compounds containing diaminomaleonitrile moieties are
prone to form intermolecular hydrogen bonds between the
amino groups and the strongly electron-withdrawing cyan
groups. Diaminomaleonitrile derivatives have been
[10b]
investigated as mechanoluminescent materials.
In the
present study, a TPE-modified diaminomaleonitrile derivative,
TPE-MN, was synthesized and the synthetic scheme is shown
in Figure 1. Hydrogen bonding assisted with loosely packing
sandwich-type crystal structure was achieved. The
mechanoluminescent properties and irradiation-induced internal motions. The emission band of TPE-MN in the
emission properties were investigated in the loosely packing aggregate state most likely originates from the intramolecular
crystals. Various photophysical studies, DSC studies and charge transfer (ICT) transition, owing to the push-pull
powder x-ray diffraction (pXRD) studies were carried out to characteristics of the TPE unit (donor) and the
investigate the relationship between the multi-responsive diaminomaleonitrile unit (acceptor).[10b]
properties and the loosely packing configuration.
Single crystal structure analysis. Single crystals of TPE-MN were
Result and Discussion
Experiment details
obtained by recrystallization from dichloromethane and
hexane mixed solvent system (CCreDC number: 1497597). The
emission intensities of AIE-active materials usually stronger in
their crystalline state than solids in the amorphous state.[1b,7]
This is mainly ascribed to the more rigid packing mode in the
crystalline state. However, the fluorescence of TPE-MN is
almost quenched in the crystalline state compared to the
emissive aggregates formed in 90% water/THF mixed solvent
system. Therefore, the fluorescence quenching process for the
TPE-MN crystals was sought. Single crystal analysis was carried
out for TPE-MN and the single crystal structure of TPE-MN is
based on the P-1 space groups. A sandwich structure can be
observed in the view down in the b axis (Figure 3a). For the
sandwich structures, TPE moieties are stacked tightly, which
can be considered as the “hard-layer”, while the
diaminomaleonitrile moieties are packed loosely together
Electronic absorption studies. Dissolution of compound TPE-MN in
dichloromethane solvent gives a pale-yellow solution at 298 K. The
UV-vis absorption spectrum is shown in Figure 2(a) and shows two
absorption bands at ca. 317 nm and ca. 391 nm. According to
previous studies, the higher energy absorption band at ca. 317 nm
is mainly attributed to the * transition whilst the lower energy
absorption band at ca. 391 nm mainly originates from
intramolecular charge transfer between the tetraphenylethylene
and the diaminomaleonitrile moieties.[10b,11]
Aggregation Induced Emission Studies. TPE is a typical AIE-active
unit, in which its enhanced emission properties in the solid-
state, compared to the dilute solution-state, is mainly
attributed to the rotations and vibrations of the phenyl
rings[7,8] With regards to TPE-MN, AIE properties can also be
…
acting as the “soft-layer”. In the “soft layer”, two CH CN
…
hydrogen bonds and one NH CN hydrogen bond, with
observed by recording the emission spectra after the gradual
addition of water to a dilute solution of TPE-MN in THF (Figure
distances of 2.72 Å, 2.74 Å and 2.09 Å, respectively, are formed
between connected TPE-MN molecules (Figure 3(b)).
2
).
2
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DOI: 10.1039/C7TC03404K
Figure 3. (a) Single crystal structure of TPE-MN; (b) the details of TPE-MN dimer with hydrogen bonding; (c) details of the repeat
units for the layer-structure.
By forming these intermolecular hydrogen bonds in the soft- also enhanced with decreasing temperature due to restriction
layer, which could lower the energies of the aggregated of molecular vibrations, however, in contrast to TPE-MN
systems, it is possible to avoid the tight packing modes in the crystals no emission “turn-on” process is observed due to
crystalline state and form loosely packing structures. According significant emission observed at 293 K. Therefore, the internal
to the single crystal analysis, the distance between the molecular motions in the loose packing areas of the crystalline
repeating units in the layered crystal structure is 10.58 Å, state lead to the emission quenching in the crystalline state,
which is much larger than the diameter for the phenyl ring (ca. which is in accordance with the mechanism of the AIE
5
.8 Å). For crystals based on traditional AIE-active TPE phenomena.
derivatives, empty areas with the diameter larger than the
diameter of phenyl ring is hardly observed. [7-9] This large
distance could provide enough space for significant
intramolecular rotations/vibrations to occur even in the solid-
state, and not just in the solution-state. In the previous
literature reports, several porous or loosely packing crystals
were also formed with the assistance of hydrogen
bonding.[6,12] The loosely packing areas in the crystal structure
might be sufficient space for the internal molecular motions to
be significant, causing the excited molecules to decay non-
radiatively to the ground state. According to the previous
literatures, the intramolecular rotations and vibrations can be
restricted with decreased temperature.[13] Therefore,
temperature-dependent emission studies were performed for
TPE-MN to further demonstrate the emission quenching
process is attributed to the molecular vibrations in the loosely
packing areas in the crystalline state. For the non-emissive
TPE-MN crystals, if the fluorescence quenching process is due
to intramolecular rotations/vibrations, the emission band is
predicted to be turned-on by decreasing the temperature.
Temperature-dependent emission spectra for TPE-MN crystals
were measured from 300 K to 145 K. As shown in Figure 4, no
obvious emission band is detected when the temperature is
above 300 K. When the temperature decreases to 200 K, the
emission is turned on, and the intensities further drastically
increase by decreasing the temperature further (up to 145 K).
The temperature-dependent emission spectra of TPE-MN in
the amorphous state (after grinding) upon cooling below room
temperature is shown in Figure S2. The emission intensities are
Figure 4. Temperature-dependent emission spectra of TPE-MN
in the crystalline state, with excitation wavelength = 365 nm.
Mechanoluminescent Properties Studies. Constructed by the
weak intermolecular hydrogen bonding, the loosely packing
crystals with sandwich-type structure might easily collapse by
mechanical force. In the AIE studies discussed previously, TPE-
MN aggregates formed in solvent/anti-solvent (THF/water)
systems were emissive. In contrast to the AIE studies, loosely
packing TPE-MN crystals are nearly non-emissive. These TPE-
MN crystals are shown to be “turn-on” mechanoluminescent
materials. As shown in Figure 5(d), the characteristic peaks for
the original crystalline TPE-MN pXRD spectrum are quite in
accordance with the simulated pXRD spectrum. This reveals
that the crystalline structures of the original TPE-MN crystals
and the single crystal of TPE-MN are identical. Emission
spectra and photographs of the turn-on and quenching
processes are shown in Figure 5(a). After grinding, the non-
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emissive TPE-MN crystals become emissive with the
emergence of a new emission band at ca. 561 nm originating
from ICT transitions. The fluorescence quantum yield increases
from <0.1% for TPE-MN in loosely packing crystalline state to
View Article Online
DOI: 10.1039/C7TC03404K
5
.4% after grinding. Therefore, the fluorescence quenching
process is attributed to the formation of the loosely packing
crystal structures. In addition, the emission of ground TPE-MN
can be quenched by heating or dichloromethane fuming
(Figure 5(b)). DSC studies have been carried out on TPE-MN in
the crystalline state and on ground TPE-MN, and the DSC scans
are shown in Figure 5(c). For the ground TPE-MN, a glass
o
transition temperature (Tg) is detected at ca. 110 C but not in
the crystalline sample, which demonstrates the morphology of
TPE-MN changes from crystalline to amorphous after grinding.
A temperature-dependent emission study for ground TPE-MN (from
3
03 K to 383 K) in the amorphous state was carried out. When the
temperature increases from 300 K to 383 K the emission intensity
for ground TPE-MN gradually decreases and finally quenches when
the temperature reaches the T (383 K). After heating to the T , the
g g
emission properties of ground TPE-MN are quite similar to that of
TPE-MN in the crystalline state. This suggests that as the material is
g
heated to its T crystallization takes place due to thermal expansion
and decrease in viscosity, which aids nucleation of the amorphous
material with subsequent reduction in emission intensity. To
further demonstrate the turn-on emission properties are
considerably related to the loosely packing crystal structure,
pXRD measurements were carried out for TPE-MN samples
after different treatments (Figure 5d). According to the Bragg
Figure 5. (a) Emission spectra of TPE-MN crystals before and
after grinding, excitation wavelength = λ = 365 nm. The inset
shows the fluorescence photographs (under UV light) of the
original and ground samples; (b) Emission spectra of ground
TPE-MN sample, dichloromethane fumed ground sample and
o
heated ground sample (to 200 C). (c) DSC spectra for the first
heat processes of TPE-MN in the crystalline state and ground
TPE-MN. (d) pXRD spectra of TPE-MN samples in the crystalline
state (original), ground TPE-MN crystals, dichloromethane
fumed ground TPE-MN sample, heated ground TPE-MN sample
o
(
to 200 C) and the simulated pXRD spectrum from the single
crystal structure.
equation, the diffraction peak of 2

= 4.1o and 8.3o
corresponds to a distance of 10.6 Å. According to the single
crystal structure, the distance between the repeat units in the
loosely packing crystals is 10.6 Å (Figure 3). Therefore, the
crystal structure is damaged after grinding. However, the
defined peaks in the pXRD spectra can be partly reversed after
heating or dichloromethane fuming. These changes further
indicate that grinding/fuming and grinding/heating can
damage or partly reconstruct the loosely packing crystal
structures and thus drastically change the emission properties
of the solid-state. By comparing the normalized emission
spectra of TPE-MN in the crystalline state, ground TPE-MN,
dichloromethane fumed ground TPE-MN and heated ground
TPE-MN (Figure S4), it can be observed that the emission of
the original crystalline sample can be recovered to some
extent after dichloromethane fuming or heating. In accordance
with the pXRD results (Figure 5(d)), the loosely packing crystal
structure was only partly recovered during the heating or
dichloromethane fuming processes. From these results above,
it can be concluded that the loosely packing crystal structure,
which provide sufficient space for the occurrence of significant
internal molecular motions, can be easily damaged/ partly
reconstructed by mechanical forces/solvent fuming.
o
o
peaks of 2
 = 4.1 and 8.3 can be tentatively assigned to the
layer distance. Consistent with the emission changes, all these
o
o
sharp peaks including the peaks of 2 = 4.1 and 8.3 in the
pXRD spectra for the original loosely packing TPE-MN crystals
disappear after grinding revealing that the loosely packing
Mechanoluminescent
properties were achieved
by
manipulating the aggregation states between crystalline and
amorphous.
4
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o
Irradiation-Induced Emission Properties Studies. In TPE-MN, the 8.3 , which were assigned as the distance between repeat
View Article Online
TPE unit is connected to diaminomaleonitrile by a C=N bond. units of the loosely packing layer structu
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For the C=N bond, cis-trans isomerization occurs by UV-light irradiation. These results demonstrate that the crystal
irradiation according to the previous literature.[14] Based on structure is maintained after irradiation. On the contrary,
o
o
o
this type of cis-trans isomerization, many photoresponsive some peaks such as 2
 = 15.5 , 17.6 and 27.2 are diminished,
materials have been designed and developed.[15] In the which indicates selective destruction of certain ordered
solution- state both the cis-isomer and trans-isomer (majority) packing in the TPE-MN crystals, which is in accordance with
1
can be observed in the H NMR spectrum (Figure S5). UV-vis the prediction above. Without the orderly packing in the soft-
absorption studies were performed for TPE-MN before and layer, the intermolecular rotations and vibrations are resisted
after UV-light irradiation at 365 nm. As shown in Figure S6, the to some extent and the emission is turned on. The photo-
lower-energy absorption band is maintained whilst the higher- responsive property is irreversible and the enhanced emission
energy absorption band, which is assigned to the  after UV-light irradiation is maintained without any reversal
transition of the TPE-MN molecule, slightly increases. For the back to the original species with comparatively lower emission
cis-trans isomerization, the cis-isomer usually displays a larger intensity. The trans to cis transition merely aids the disordering
extinction coefficient for the  transition.[14a] The slight of the well-aligned diaminomaleonitrile moieties with emission
enhancement of the higher-energy absorption band could be always originating from the trans isomer due to the rapid cis to
ascribed to the increased amount of the cis-isomer after UV- trans back conversion after UV-light irradiation has stopped.
light irradiation. However, this is only cautiously reported due
to the fast reverse isomerization from cis to trans after UV-
light irradiation has ceased. In previous reports, some
tetraphenylethylene and triphenylethylene derivatives display
photo-responsive properties due to photocyclization
reactions.[16] These materials display drastic color changes
after irradiation, which is mainly due to the enhanced
molecular conjugation after the photocyclization. To exclude
the possibility that the photo-responsive properties are caused
by photocyclization, UV-vis reflectance spectra were measured
for TPE-MN in the crystalline state before and after UV-light
irradiation. As shown in Figure S7, no new absorption bands
can be detected after irradiation. The absorption band around
Figure 6. (a) Emission spectra of TPE-MN crystals before and
after UV-light irradiation at 365 nm, excitation wavelength =
3
65 nm. The inset shows the fluorescence photographs (under
4
50 nm is slightly enhanced, which is mainly due to the
UV-light) of the original and irradiated samples. (b) pXRD
spectra of TPE-MN in the crystalline state before and after
irradiation.
increased amount of the cis-isomer after UV irradiation as
mentioned above. This result can preclude the possibility that
the photo-responsive properties of TPE-MN were caused by
photocyclization or photooxidation. In the crystalline state, the
well-aligned diaminomaleonitrile moieties might become
disordered by UV-light irradiation and thus the emission is Conclusions
turned on by breaking the well-aligned loosely packing soft- Loosely packing molecules in the crystalline state with sandwich-
layer.
type structure has been demonstrated for compound TPE-MN. The
loosely packing mode was formed with the assistance of
Similar to the predicted results, the non-emissive TPE-MN intermolecular hydrogen bonding. With the loose-packing mode,
crystals become emissive with enhanced emission intensity the diaminomaleonitrile moiety of TPE-MN can rotate and vibrate
and emission maximum at ca. 563 nm after UV-light and, therefore, fluorescence quenching in the crystalline state is
irradiation, as shown in Figure 6(a). The emission spectra for observed. By destroying the loose-packing mode with mechanical
the ground sample before and after UV-light irradiation were force, the emission properties can be significantly enhanced (turn-
also measured. After the grinding process the crystal structure on). Oppositely, by solvent fuming or heating the emission can be
has already been destroyed due to a crystalline to amorphous turned-off. Moreover, by selectively breaking the orderly packing
morphology transition, therefore, the enhancement of mode of the soft layer in the crystals by UV-light irradiation, the
emission intensity for ground TPE-MN cannot be observed emission can also be turned on. These results provide a new
after irradiation (Figure S8). To further investigate the strategy to design multi-responsive materials with turn-on emission
irradiation-induced emission properties, pXRD studies were properties by combining AIE-active molecules and loosely packing
performed on the TPE-MN crystals before and after irradiation crystal structures.
(
Figure 5(b)). It can be observed that most of the peaks are still
o
sharp after irradiation. Especially the peak at 2

= 4.1 and
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Krishna, H. Wu, W. Zhou, M. O’Keeffe, Y. Han VaienwdArBtic.leCOhnelinne,
Acknowledgements
Angew. Chem., Int. Ed., 2015, 54, 574.
DOI: 10.1039/C7TC03404K
The authors gratefully acknowledge the financial support from 7 J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, C. Qiu, H. S. Kwok, X. Zhan,
D. Liu, D. Zhu and B. Z. Tang, Chem. Commun., 2001, 18, 1740.
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Program (SS2015AA031701), the Fundamental Research Funds
for the Central Universities, Guangdong Science and
Technology Plan (2015B090913003, 2015B090915003,
8
9
1
Hong, J. W. Y. Lam and B. Z. Tang, Chem. Commun., 2009, 29
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017As0310295), CSC project (201506385012) and supports
from Educational Commission of Guangdong Province
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Journal of Materials Chemistry C
View Article Online
DOI: 10.1039/C7TC03404K
Title: Hydrogen-Bonding Assisted Loosely Packing Crystals of a Diaminomaleonitrile-modified
Tetraphenylethene Compound and their Photo- and Mechano-Responsive Properties
Loosely Packing Crystals: This study reveals that loosely packing crystals can be constructed with the
assistance of intermolecular hydrogen bonding. Combined with a traditional AIE building block,
loosely packing crystals can be used as multi-responsive materials with turn-on emission properties.