Inclusion induced second harmonic generation in low dimensional supramolecular crystals

Article abstract of DOI:10.1039/c3tc31399a

A host-guest inclusion complexation self-assembly strategy was developed for the synthesis of SHG-active low dimensional supramolecular crystals (LDSCs). p-Nitroaniline guest molecules with high inherent second-order polarizability were introduced into the cavities of the β-cyclodextrin host to form supramolecular inclusion complexes, which were then assembled into microscale crystalline structures with an anti-solvent diffusion combined solvent-evaporation-induced self-assembly method. Two distinct types of LDSCs with controllable dimensions were obtained by altering the polarity of anti-solvents and the concentration of supramolecular monomers. Each type of LDSCs exhibited its characteristic SHG response to the polarized incident signals, which is attributed to the inherent crystal structures. This journal is the Partner Organisations 2014.

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Graphical and Textual Abstract
Inclusion Induced Second Harmonic Generation in Low
Dimensional Supramolecular Crystals
5
Jianmin Gu, Yongli Yan, Chuang Zhang, Jiannian Yao and Yong
Sheng Zhao*
1
0
A host-guest inclusion complexation self-assembly strategy of breaking
crystalline centrosymmetric geometry in aromatic derivatives was developed to
generate SHG active low dimensional supramolecular crystals.
1
5
2
0

Journal of Materials Chemistry C
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DOI: 10.1039/C3TC31399A
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ARTICLE TYPE
Inclusion Induced Second Harmonic Generation in Low Dimensional
Supramolecular Crystals
Jianmin Gu, Yongli Yan, Chuang Zhang, Jiannian Yao and Yong Sheng Zhao*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
A hostꢀguest inclusion complexation selfꢀassembly strategy was developed for the synthesis of SHGꢀ
active low dimensional supramolecular crystals (LDSCs). pꢀNitroaniline guest molecules with high
inherent secondꢀorder polarizability were introduced to the cavities of βꢀcyclodextrin host to form
supramolecular inclusion complexes, which were then assembled into microscale crystalline structures
with an antiꢀsolvent diffusion combined solventꢀevaporationꢀinduced selfꢀassembly method. Two distinct
types of LDSCs with controllable dimensions were obtained by altering the polarity of antiꢀsolvents and
the concentration of supramolecular monomers. Each type of LDSCs exhibited its characteristic SHG
response to the polarized incident signals, which is attributed to the inherent crystal structures.
1
0
molecules to obtain ordered aggregates with desired optical
2
0ꢀ22
Introduction
properties.
The hostꢀguest inclusion techniques based on
supramolecular recognition have been successfully used to
construct the noncentrosymmetric materials for NLO
applications.
guest molecules are completely separated from each other to
avoid molecular centrosymmetric aggregation, which has a
beneficial effect for the NLO activity. Moreover, it is convenient
to modulate the NLO properties of supramolecular materials by
controlling the hostꢀguest inclusion process.
Herein, we demonstrate a hostꢀguest inclusion complexation
selfꢀassembly strategy of breaking crystalline centrosymmetric
geometry in aromatic derivatives to synthesize SHGꢀactive low
dimensional supramolecular crystals (LDSCs). First, the guest
molecules were inserted into the host molecules to form 1:1 hostꢀ
guest inclusion complex. By using the inclusion complex as
building blocks, we synthesized two distinct types of low
dimensional supramolecular crystals with an antiꢀsolvent
diffusion combined solventꢀevaporationꢀinduced selfꢀassembly
method. These supramolecular crystals were observed to produce
efficient SH radiation when exposed to the fsꢀpulsed Ti:sapphire
laser. Polarization measurements of the SHG signal indicated that
the two types of LDSCs exhibited different SHG responses,
which is attributed to the distinct inherent crystal structures. The
results might offer comprehensive understanding of the inducing
mechanism of SHG and give a useful enlightenment for the
development of low dimensional organic NLO materials for
nanophotonic devices.
1
2
2
3
3
4
4
5
0
5
0
5
0
5
Nanometreꢀscale photonics is emerging as a key ingredient in
novel sensing and imaging applications, as well as for advanced
information technology, cryptography and signal processing
5
5
6
6
7
0
5
0
5
0
23ꢀ27
The important merit of the inclusion state is that
1
circuits. One crucial challenge for nanophotonics is to develop a
28
coherent laser radiation source. Second harmonic generation
(SHG) is a nonlinear optical (NLO) process which leads to the
generation of new output with frequency twice of the incident
2
3
laser radiation. Unlike common linear optical process, SHG
provides a possible way to accomplish frequency conversion of
coherent light with the essentially independent of the incident
4
5
wavelength, high polarization selectivity and the temporal
6
response time. In recent years, the low dimensional structured
materials have been showing great promise as the potential SHG
media for applications in integrated photonics due to their wide
range of emission frequencies, less stringent phase matching
conditions and high photochemical stability.
great scientific interest and technological significance to develop
the nanostructured SHG materials that exhibit a strong nonlinear
optical response.
Organic materials are inherently good candidates for SHG
applications over the inorganic counterparts because of their
high optical nonlinearities, fast response time, high damage
7
8
ꢀ12
Therefore, it is of
1
3
1
4,15
threshold and ease of design and fabrication.
most of organic molecules crystallize in centrosymmetric space
groups, thus producing materials with no SHG activity.
Unfortunately,
16
Methods for achieving the arrangement of organic molecules in
acentric environments are mainly focused on LangmuirꢀBlodgett
7
5
Experimental
1
7
18
technique, electric field poling process, or liquidꢀcrystal
1
9
ordering strategy. However, these methods are usually either
too complicated or unfit for achievement of the SHG materials
with high stability. Supramolecular selfꢀassembly represents a
process for easily controlling the packing and orientation of
Preparation of low dimensional supramolecular crystals
pꢀnitroaniline (PNA) and βꢀcyclodextrin (βꢀCD) were
purchased from SigmaꢀAldrich and used without further
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DOI: 10.1039/C3TC31399A
purification. The LDSCs were prepared through an antiꢀsolvent
order nonlinear optical properties. This result will help us to
understand the effects of βꢀCD host on the packing of PNA guest
and the origin of nonlinear optical properties in this system.
The PNA aqueous solution with variable amount of βꢀCD was
kept under vigorous stirring overnight to form the complex. Fig.
diffusion combined solventꢀevaporationꢀinduced selfꢀassembly
method. In a typical preparation, 10 mL of PNA (0.01 M)
aqueous solution was added to 10 mL of aqueous solution
containing 0.1 mmol of βꢀCD. The solution was kept under
vigorous stirring overnight to form stable 1:1 PNA@βꢀCD
inclusion complex. Then several drops of the PNA@βꢀCD
solution was dripped onto a quartz substrate, which was placed in
60
5
0
5
1b shows the UVꢀvis spectra of PNA in H O at various βꢀCD
2
concentrations. The absorption maximum at 380 nm is shifted by
3ꢀ5 nm to longer wavelengths along with the enhancement of the
a beaker (20 mL) containing 3 mL antiꢀsolvent. The water and 65 absorption intensity as
a
function of increased βꢀCD
3
6
1
ethanol were selected as the antiꢀsolvents to synthesize the
channelꢀ and cageꢀtype LDSCs, respectively. In the whole
procedures, a solvent atmosphere was created and the evaporation
speed of the solvent (i.e. the saturation degree of the solution)
could be well controlled. With a selfꢀassembly of the PNA@βꢀ
concentration, suggesting the formation of PNAꢀβꢀCD complex.
The stoichiometry of the complex is determined according to the
BenesiꢀHildebrand equation (1),
37
n
0
1
/ꢀA =
(
1/ꢀ
ε
∗ L∗
[G
]
∗ Kn
)
∗
(
1/
[H
]
)
+1/ꢀ
ε
∗ L∗
[G
]0
(1)
0
1
CD molecules in the beaker for 2ꢀ3 days, largeꢀarea LDSCs were 70 where [G]0 is the total concentration of PNA, [H] is the
0
finally obtained. Then, the resulted products were dried in a
vacuum oven for 4 h at 60 °C to remove the residual solvent prior
to characterizations.
concentration of βꢀCD, n is the βꢀCD molecular ratio in the
complexes, K is the complex stability constant, L is a constant in
n
the experiment, ꢀε is the difference of the molar absorptivities
between free and complexed PNA, and ꢀA is the change in
absorbance by the addition of βꢀCD. The plot of 1/ꢀA versus
1/c[βꢁCD] shows excellent linear fit (Fig. S2), indicating that the
molecular ratio of PNA to βꢀCD in the complex is 1:1.
Measurements
7
8
8
9
5
0
5
0
20
25
30
35
40
The LDSCs were characterized with SEM (Hitachi Sꢀ4300),
TEM (Tecnai F20) and XRD (Philips X’pert PRO), respectively.
The UVꢀvisible spectra were measured on a SHIMADZU UVꢀ
3
600 spectrophotometer. Circular dichroism spectra were carried
1
out on a JASCO Jꢀ815 CD spectropolarimeters. The H NMR
spectra were measured on a bruker AVANCE 400 MHz
spectrometer using tetramethylsilane (TMS, δ = 0 ppm) as an
internal standard and D O as solvent (4.79 ppm). The SHG
2
measurements were carried out in a backꢀscattering geometry
using an inverted microscope (Nikon, TiꢀU). Fig. S1 (See ESI†)
shows the scheme of the setup. A 830 nm pulsed Ti:sapphire laser
(SpectraꢀPhysics) with a repetition rate of 80 MHz and duration
of 100 fs was focused to a beam spot size of 2 ꢁm to excite single
LDSCs using an objective lens (Nikon CFLU Plan, 50×, N.A. =
0
.8). The SHG emission spectra were measured as a function of
the angle between the long diagonal axis of rhombusꢀshaped
LDSC and the incident electric field vector, which was tuned by a
halfꢀwave plate. The intensity of the fundamental beam was
varied by rotating a round variable neutral density filter and was
Fig. 1 (a) Molecular structures of pꢀnitroaniline (PNA) and βꢀcyclodextrin
monitored by a power meter. The fundamental beam passing 95 (βꢀCD). (b) UVꢀvis spectra of PNA in H O with various concentrations of
2
ꢀ5
βꢀCD. The concentration of PNA is kept constant of 6×10 M with
through the sample was rejected by an appropriate filter, and the
generated bright SHG signal was recorded with a CCD (ProEm,
Princeton Instruments) after dispersed by a monochromator (SPꢀ
ꢀ3
1
different concentrations of βꢀCD (0 ~ 2×10 M). (c) H NMR spectra
400 MHz) of the PNA, βꢀCD and PNA@βꢀCD inclusion complex in
O. (d) Circular dichroism spectrum of the PNA@βꢀCD inclusion
(
D
2
2
358, Acton). All experiments were carried out at room
1
00 complex. Inset: Schematic illustration for the molecular structures of the
temperature and atmospheric pressure.
inclusion complex.
1
The H NMR spectra (Fig. 1c) of PNA, βꢀCD and the complex
45
Results and discussions
show that the chemical shifts of βꢀCD interior protons, H and H ,
3
5
The aromatic derivative pꢀnitroaniline (PNA) (Fig. 1a) was
move upfield by about 0.04 ppm upon complexation, while the
selected as model molecular systems for SHG study due to its 105 exterior protons, H , H , H and H , are relatively unaffected.
1
2
6
4
2
9
high inherent secondꢀorder polarizability. However, the PNA
molecules fail to be SHG active in the solid materials because
their crystal space group is centrosymmetric. Therefore, βꢀ
cyclodextrin (βꢀCD) (Fig. 1a) was chosen as the host molecule to
These results clearly indicate that the PNA molecule is
successfully included in the βꢀCD cavity to form the PNA@βꢀCD
38
50
inclusion complex. The chemical shifts of the PNA protons in
the low field region, H , move upfield by about 0.03 ppm, but H
2
1
3
0ꢀ32
induce SHG
since its hydrophobic cavity had a remarkable 110 remain unshifted, which suggests that the PNA molecule enters
ability to incorporate various organic molecules to form the
the βꢀCD cavity preferentially from the secondary hydroxyl group
side with inserting the nitro group first. The circular dichroism
3
3ꢀ35
38
inclusion complex.
The complex can be subsequently used as
55
building blocks to construct microscale noncentrosymmetric
supramolecular crystals, which are expected to exhibit secondꢀ
spectrum of the inclusion complex is shown in Fig. 1d. The long
1
wavelength absorption band ( L ) of PNA exhibits an intense,
b
2
| Journal Name, [year], [vol], 00–00
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DOI: 10.1039/C3TC31399A
39
positive sign upon inclusion. According to Harata’s rule, the 60 and d reveal that the edge angle of the WꢀLDSCs and EꢀLDSCs is
circular dichroism sign of a molecule located inside the βꢀCD
cavity will always be positive when its electric transition dipole
moment is parallel to the axis of βꢀCD. Therefore, the long
74° and 60°, respectively. Selected area electron diffraction
(SAED) patterns show that the two types of LDSCs are both
singleꢀcrystalline.
5
0
5
0
5
0
molecular axis of PNA, which is aligned with the transition
moment of the Lb band, is parallel to the βꢀCD axis. The 65 is schematically illustrated in Fig. 2e. First, PNA molecules were
schematic structure of the PNA@βꢀCD inclusion complex is
shown in the inset of Fig. 1d.
The formation mechanism of the two distinct types of LDSCs
1
included in the βꢀCD cavities to form 1:1 PNA@βꢀCD inclusion
complex. With the evaporation of the solvent, inclusion
molecules aggregate to form small nuclei. The vapor pressure of
the antiꢀsolvent allows a continuous dissolutionꢀequilibrium for
nuclei, enabling them to grow slowly and recrystallize stepꢀbyꢀ
step to form 2D microstructures with minimal crystalline defects.
1
1
2
2
3
7
7
8
8
0
5
0
5
42
According to ‘like dissolves like principle’, the polarity of the
antiꢀsolvent can influence solubility of the molecules and thus
allow for the optimization of the selfꢀassembly process. When the
PNA@βꢀCD aqueous solution was dripped into the atmosphere
of ethanol, the ethanol molecules diffused into the solution
rapidly, which causes molecular segregation and rearrangement
due to the significant polarity difference between the two solvents
and therefore change the final packing conformation of the
43
crystals.
90
Fig. 2 (a, b) SEM images of the WꢀLDSCs and EꢀLDSCs, respectively.
Scale bars are 20 ꢁm. (c, d) TEM images of the WꢀLDSCs and EꢀLDSCs,
respectively. Scale bars are 3 ꢁm. The edge angle of the WꢀLDSCs and Eꢀ
LDSCs is 74° and 60°, respectively. Insets are the selectedꢀarea electron
diffraction (SAED) patterns of the corresponding samples. (e) Schematic
depiction of the formation mechanism for the two distinct types of
LDSCs.
3
4
5
0
Fig. 3 (a) SH emission spectra of the single WꢀLDSC and EꢀLDSC under
the illumination of the fundamental wave of 830 nm from a fsꢀpulsed
Ti:sapphire laser. (b, c) The excitation power dependence of the SH
intensity of the WꢀLDSCs and EꢀLDSCs. The data fits a slope of two,
proving the secondꢀorder nature of the emitted light. (d) Schematic of the
experimental setup for polarization experiments. A single LDSC is
95
1
1
00 excited with a linearly polarized laser beam (830 nm). The sample is
placed in the XY plane and the excitation laser propagates in the Z
direction. θ refers to the angle between the incident light polarization and
the long diagonal axis of the rhombusꢀshaped LDSCs. (e, f) Polar plots of
the SHG signal as a function of the incident polarization angle from the
05 single WꢀLDSC and EꢀLDSC, respectively.
By using 1:1 PNA@βꢀCD complex as building blocks, we
synthesized the low dimensional supramolecular crystals with an
antiꢀsolvent diffusion combined solventꢀevaporationꢀinduced
4
0,41
selfꢀassembly method.
Several drops of the PNA@βꢀCD
4
5
5
5
0
5
solution was dripped onto a quartz substrate, which was placed in
a beaker containing the antiꢀsolvent. The LDSCs were produced
by molecular selfꢀassembly under a certain antiꢀsolvent pressure.
We selected water (polarity index 10.2) and ethanol (polarity
index 4.3), respectively as the antiꢀsolvents. When water was
The low dimensional structured materials fabricated from the
molecules with high optical nonlinearities may offer a model
system for the study of secondꢀorder nonlinear optical properties.
The SHG measurement of a single LDSC was performed in a
applied, the rhombusꢀshaped LDSCs were obtained on a large 110 backꢀscattering geometry (Fig. S1) under the illumination of the
scale as shown in Fig. 2a (called waterꢀinduced LDSCs, Wꢀ
LDSCs). With the concentration of the solution increasing from 2
to 5 mM, the edge length of the WꢀLDSCs grew from 6 to 15 ꢁm
fundamental wave of 830 nm from a fsꢀpulsed Ti:saphire laser.
The laser beam with average pump power of 3 mW was focused
to a laser spot size of 2 ꢁm on a single LDSC. The SHG signal
was recorded with a CCD after dispersed by a monochromator.
15 The SH emission spectra of the single WꢀLDSC and EꢀLDSC
shown in Fig. 3a indicate that the SH intensity of the WꢀLDSC is
stronger than that of the EꢀLDSC. The power dependence of the
SH signals from the WꢀLDSCs and EꢀLDSCs are shown in Fig.
(Fig. S3). When the antiꢀsolvent was changed to ethanol, the
obtained LDSCs (called ethanolꢀinduced LDSCs, EꢀLDSCs)
became larger and changes also occurred in the edge angle of the
rhombus (Fig. 2b). The SEM images (Fig. S4) show that the size
of the EꢀLDSCs can also be controlled by tuning the
concentration of the solution. The TEM images shown in Fig. 2c
1
3
b and c, respectively. The intensities increase linearly with
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C3TC31399A
n
excitation intensity Iω (n = 2.01 for WꢀLDSCs, and 2.04 for Eꢀ 60 clearly reveals that the asꢀprepared nanostructures are
LDSCs), further confirming secondꢀorder nature of the emitted
light.
supramolecular crystals rather than the simple mixture of βꢀCD
and PNA. There are clear differences in the XRD patterns of the
WꢀLDSCs and EꢀLDSCs. The strong diffraction peak of 11.8° is
observed for WꢀLDSCs, which is the characteristic peak of
The specific molecular orientation in inclusion complex
crystals might result in a strong polarization dependence of the
5
0
5
0
5
0
5
0
44ꢀ46
53
SHG signals.
Here the polarization response of the SHG 65 channelꢀtype inclusion crystals. However, the XRD patterns of
signals was investigated by rotating the Eꢀfield direction of the
excitation laser. Fig. 3d shows a typical experiment, in which a
single LDSC was excited with a linearly polarized laser beam
(830 nm). The parameter θ refers to the angle between the long
the EꢀLDSCs possess the orthorhombic features, in which the
molecules align nonꢀcoaxially to form the cageꢀtype structure.
As shown in Fig. 4b, the two types of LDSCs both exhibit
induced circular dichroism with an intense, positive sign, which
5
4
1
1
2
2
3
3
4
diagonal axis (Y) of the rhombusꢀshaped LDSC and the incident 70 indicates the noncentrosymmetric structure of the supramolecular
electric field vector E , which was adjusted using a halfꢀwave
crystals. The different ellipticity of the two types of LDSCs
indicates different stacking degree of the molecules in
0
plate. Fig. 3e and f show the polar variation of the SH signals as a
function of the polarization direction from the single WꢀLDSC
and EꢀLDSC, respectively. The SH intensities of a single LDSC
varied in an oscillatory manner between a maximum (‘on’ state)
5
5
supramolecular crystals, which leads to the distinct SHG
responses in the WꢀLDSCs and EꢀLDSCs.
75
The difference in the SHG responses for the two types of
LDSCs is attributed to the distinct inherent crystal structures,
which are schematically illustrated. In the PNA crystals (Fig. 4c),
two PNA molecules are in an antiꢀparallel centrosymmetric
arrangement and the adjacent dipoles tend to cancel each other to
and minimum value (‘off’ state). It follows
a twoꢀlobe
polarization pattern, indicating that PNA molecule is oriented in
straight dipole chains along specific crystallographic direction of
4
7ꢀ49
the low dimensional supramolecular crystals
(See Theory in
ESI†). The maximum in SH emission was observed at 80 destruct the SHG. In the channelꢀtype LDSCs, βꢀCD molecules
polarization angle θ of 0° (also 180°) for WꢀLDSC, while it was
observed at θ of 45° (also 225°) for EꢀLDSC, implying distinct
PNA molecular orientations in these crystals. Moreover, the
on/off ratio R = I2ω, max/I2ω, min of the WꢀLDSC and EꢀLDSC is
are coaxially stacked to form linearly aligned, endless channels,
in which PNA molecules are embedded, as shown in Fig. 4d. For
the cageꢀtype structures (Fig. 4e), βꢀCD molecules are packed
crosswise in a herringbone fashion and the βꢀCD cavity is
determined to be 4.67 and 3.59, respectively. A polarization ratio 85 blocked off on both sides by adjacent βꢀCDs, thereby leading to
4
1
(
ρ) is defined as ρ = (R−1)/(R+1), which is used for a
the isolated cavities. The additive interaction of PNA molecules
in the channelꢀtype structures is possible to maximize the secondꢀ
order nonlinearity, while partial molecules orientation
cancellation occurs to reduce optical nonlinearity in the cageꢀtype
structures. The difference in the stacking forms of the inclusion
supramolecules in WꢀLDSCs and EꢀLDSCs produces distinct
PNA molecular orientations, which leads to different angular
quantitative analysis of the modulation of the emitted light. Here,
ρ = 0.65 is obtained for WꢀLDSC, which is larger than those of
5
0,51
the previously reported results.
90
56
polarization dependence of the SHG signals.
Conclusions
95
In conclusion, we have developed a hostꢀguest inclusion
complexation selfꢀassembly approach for the synthesis of the two
types of low dimensional supramolecular crystals (LDSCs).
These LDSCs are capable of exhibiting effective SHG activity
because of their noncentrosymmetric arrangement. The two types
1
00 of LDSCs exhibit different SHG responses, which is determined
by the distinct inherent crystal structures. The synthesis strategy
reported here is promising as a versatile technique for the
preparation of supramolecular nanomaterials, which will provide
valuable idea for the development of NLO materials. These low
05 dimensional structured materials could serve as a promising
nanophotonics device, with numerous potential applications
ranging from a variable intensity source of SHG laser to the
creation of locally coherent light sources that could be employed
in labꢀonꢀaꢀchip task.
45
1
Fig. 4 (a) XRD patterns of the PNA, βꢀCD, WꢀLDSCs and EꢀLDSCs. (b)
Circular dichroism spectra of the low dimensional supramolecular
crystals with the channelꢀ and cageꢀtype alignments, which indicate these
LDSCs are of noncentrosymmetric structures. (c, d and e) Schematic
illustration for the crystal structure of PNA, WꢀLDSCs and EꢀLDSCs,
respectively.
50
110 Acknowledgements
55
The efficient SHG of the LDSCs originates from unique PNA
molecular alignment in the supramolecular crystals since both βꢀ
CD crystals and PNA crystals cannot give a detectable second
harmonic signal. Fig. 4a shows the powder XRD patterns of βꢀ
CD, PNA, WꢀLDSCs and EꢀLDSCs, where their comparison
This work was supported by the National Natural Science
Foundation of China (Nos. 21125315, 51203165), the Chinese
Academy of Sciences, and the Ministry of Science and
Technology of China (2012YQ120060).
52
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2
6
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