Supramolecular structural transformation of: N, N ′-bis(4-pyridylmethyl)-naphthalene diimide and fluorescence water sensing

Article abstract of DOI:10.1039/c6nj04018g

A supramolecular structure based on N,N′-bis(4-pyridylmethyl)-naphthalene diimide exhibits reversible phase transitions in a single-crystal-to-single-crystal process. Such temperature induced SC-SC transformations are driven by intermolecular π-π interactions and hydrogen bond interaction. Interestingly, the dynamic supramolecular structure shows selective adsorption and fluorescence water sensing.

Full text of DOI:10.1039/c6nj04018g

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Supramolecular structural transformation of N, N´ꢀbis(4ꢀpyridylmethyl)ꢀ
naphthalene diimide and fluorescence water sensing
Received 00th January 20xx,
Accepted 00th January 20xx
Guo-Bi Li, ab Qing-Yuan Yang, c Rong-Kai Pan, a Sheng-Gui Liu,*a Yao-Wei Xu*b
DOI: 10.1039/x0xx00000x
Abstract: A supramolecular structure based on N, N´-bis(4-pyridylmethyl)-naphthalene diimide exhibits reversible phase
transitions in a single-crystal-to-single-crystal process. Such temperature induced SC-SC transformations are driven by
intermolecular π-π interactions and hydrogen bond interaction. Interestingly, the dynamic supramolecular structure shows
selective adsorption and fluorescence water sensing .
www.rsc.org/
compound capable of self-organisation and being incorporated
into larger multicomponent assemblies through intercalation.9
Introduction
In recent years, the design and synthesis of supramolecular
organic frameworks (SOFs) have captured the attention of
chemists because of their potential applications in the areas of
drug delivery, selective catalysis, cell mimicking,
nanotechnology, fluorescence sensor, gas sorption and
separation.1-3 SOFs can be readily self-assembled from two or
more organic species by noncovalent interactions such as
hydrogen-bonding, halogen-bonding, cation-π interactions, π-
π interactions and van der Waals forces.4-5 The components of
supramolecular organic frameworks define the shape, size,
properties of the resultant supramolecular aggregate, and play
a vital role in the functioning of the SOFs as well as in their
structural morphology.6 The π-π stacking has the relatively low
Due to their planar aromatic nature, naphthalene diimides
exhibit stacking in the solid-state with distances
commensurate with π-π stabilisation.10 Since introduction of
heteroatom nitrogen in the aromatic ring increases the
stabilization energy, significantly, the pyridine dimer has 6
kJ⋅
mol-1 higher stabilization energy than the benzene dimer,11
4-pyridylmethyl groups was placed on the diimide nitrogens to
produce highly ordered π-stacking structures.12 The π-π
interactions absorb the strain energy by adjusting their
intermolecular distances and keep the crystal packing stable
even after large deformation.13 The single-crystal-to-single
crystal (SCSC) transformation is preferred, since it allows direct
visualization of how the crystal structure is changed during the
transformation process.14-15 These direct insights further the
understanding of the subtle interaction between the guest
molecules and the host. Materials with reversible SCSC
structure transformations and characteristic responses toward
specific external stimuli are vitally important for applications in
selective adsorption and sensing for small molecules,
molecular switches, and catalysis.16-17
stabilization energy about 10kJ⋅
mol-1 and can lead to rapid
interconversion to structures, which often plays important
roles in functional molecules.7-8 The naphthalene diimides are
a compact, neutral, planar, electron deficient class of aromatic
a.School of Chemistry and Chemical Engineering, Lingnan Normal University,
Zhanjiang 524048, People’s Republic of China.
b..MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of
Optoelectronic Materials and Technologies, School of Chemistry and Chemical
Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
c. Department of Chemical Sciences, Bernal Institute, University of Limerick,
Limerick, Republic of Ireland.
Crystallographic data for the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as supplementary publication no.
CCDC 1507742-1507744. Copies of the data can be obtained free of charge from
www.ccdc.cam.ac.uk/conts/retrieving.html
Herein, we report about the remarkable structural features
and physical properties of an hydrate crystal form of N, N´-
bis(4-pyridylmethyl)-naphthalene diimide(4-pmntd), which
shows reversible SCSC structure transformations and
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characteristic responses toward water. Furthermore, the diffraction (PRXD) was recorded on a Bruker D8 ADVANCE
selective adsorption and fluorescence sensing for water were diffractometer (CuKα, 1.5418 Å) at 40 kV and 40 mA. Thermal
also studied,in the solid state.
analyses and DSC were performed on a TGA V5.1A Dupont
2100 instrument from room temperature to 800 C with a
heating rate of 10
C min-1 in the air, and the data are
°
°
Experimental
consistent with the structures. The adsorption isotherms of
CO2 (at 195 K), N2 and H2 (at 77 K) were measured by using
BELmax 00027 adsorption equipment (BEL Japan). The
methanol (298 K), alcohol (298 K) and toluene (298 K) vapor
were measured with a BELSORP-max automatic volumetric
sorption apparatus. An exactly measured amount of the
sample was introduced into the gas sorption instrument after
General procedures
All materials were reagent grade, obtained from commercial
sources, and used without further purification. Solvents were
dried by standard procedures. The 4-pmntd was prepared
from the reaction of 1,4,5,8-naphthalenedianhydride with 4-
(aminomethyl)pyridine according to previous literatures.12g
the sample was pre-desolvated in a Schlenk tube at 120 °C
under vacuum for 24 h. The adsorbate was placed into the
sample tube, then the change of the pressure was monitored
and the degree of adsorption was determined by the decrease
of the pressure at the equilibrium state. The sorption
properties were analyzed using Autosorb 1 for Windows 1.24
software.
Synthesis
[4-pmntd·2H2O] (1). A mixture of MnCl2 · 4H2O (19.8 mg, 0.1
mmol), 4-pmntd (6 mg, 0.0125 mmol), NaSCN (8.5 mg, 0.1
mmol) in H2O (1.0 mL), and CHCl3 12.0 mL) was stirred and
then sealed in a 20 mL Teflon-lined autoclave. The autoclave
X-ray crystallography
was heated to 110
°C and held at that temperature for 7 days,
followed by cooling to room temperature. Orange crystals of
1
were collected in 25% yield based on the 4-pmntd. Anal. Calcd
for C26H18N4O5: C,66.95; H, 3.89; N, 12.01%. Found: C, 66.75; H,
4.02; N, 11.86%. IR (KBr, cm-1): 3440vs, 1706m, 1667s, 1605w,
1580w, 1451w, 1416w, 1375w, 1340m, 1245m, 1116s, 1082s,
768m, 565m. Phase purity was verified by powder XRD.
The diffraction data were collected on a Oxford Gemini S Ultra
diffractometer equipped with Cu-Kα radiation (λ = 1.54178 Å)
for compounds
1
,
2
, and
3
by using φ and ω scans. Analytical
and
adsorption corrections were applied for compounds
2
3.
Multiscan adsorption corrections were applied for all others.
The structures were solved by the direct methods (SHELXS)
and refined by the full matrix least-squares method against Fo2
using the SHELXTL software.18 The coordinates of the non-
hydrogen atoms were refined anisotropically. Most of
Preparation of [4-pmntd] (
Subsequently, the desolvated crystal [4-pmntd] (
obtained by heating a single crystal at 100 C under air for a
period of 12 h. Then the single crystal exposed to air for
seven days resulted in contraction to the close packed
2) and dense [4-pmntd] (
3).
2) was
1
°
2
hydrogen atoms were introduced in calculated positions and
refined with fixed geometry with respect to their carrier atoms,
and the water hydrogen atoms have been not added. Details
of the crystal parameters, data collections and refinement for
the three compounds are summarized in Table 1. Further
details are provided in Supporting Information. The CCDC
structure crystal [4-pmntd] (3).
Physical measurements
Elemental analyses (C, H, N) were carried out with a Perkin-
Elmer 240C elemental analyzer. FT-IR spectra were recorded
from KBr pellets in the range of 4000-400 cm-1 on a VECTOR 22
spectrometer. UV-Visible absorption spectra were recorded on
a UV-2501PC UV-Visible Spectrophotometer. The powder X-ray
1507742-1507744 are for the compounds
1, 2, 3, respectively.
Table 1. Crystallographic data for 1, 2, and 3
2 | J. Name., 2012, 00, 1-3
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nearly no π-π interaction between the adjacent pyridine rings.
Hydrogen bonded water molecules reside in the channels of the 4-
Compound
Formula
1
2
3
C26 H16 N4 O4
C26 H16 N4 O4
C26 H16N4 O4.2H2O
pmntd host framework connected via water … pyridine
H
Fw
480.43
293(2)
1.54178
Monoclinic
C2/c
448.43
373(2)
1.54178
Monoclinic
C2/c
448.43
bonding( Figure 2).
T(K)
293(2)
Wavelength(Å)
Crystal system
Space group
a(Å)
0.71073
Triclinic
Pꢀ1
27.561(3)
4.6812(2)
21.646(4)
90
22.760(8)
4.6927(12)
21.335(8)
90
5.588(3)
7.545(4)
11.984(6)
77.113(11)
88.392(13)
87.412(12)
492.0(5)
1
b(Å)
Fig. 1 The structure of compound 1.
c(Å)
α(deg)
β(deg)
128.914(17)
90
115.96(5)
90
γ(deg)
V (Å3)
2173.0(4)
4
2048.8(12)
4
Z
Fig. 2 The 2D network through π-π interaction and hydrogen
bond of compound
ρcalcd(g cmꢀ3)
ꢁ(mmꢀ1)
1.468
1.454
1.514
1.
0.895
0.831
0.105
A single-crystal-to-single-crystal transformation between 1, 2, and
Reflnscollected/unique4658 / 1611
4003 / 1507
1.074
4205 / 1916
1.001
3
We suppose that the hydrate crystal form 1 may release the
GOF
1.040
water molecules without causing a collapse of the crystal
structure because of the presence of strong π-π interactions.
R1 [I > 2σ(I)]
ωR2 [all data]
0.0383
0.1045
0.1265
0.0669
0.2899
0.1164
To explore this possibility, orange single crystal
1 was heated
2
2
R1= Σ||Fo| ꢀ |Fc||/|Fo|, wR2 = [Σw(Fo2 ꢀ Fc2)2/Σw(Fo )2]1/2, where w = 1/[σ2(Fo ) +
and then analyzed. The result of temperature-dependent XRPD
measurements exhibit that the framework is robust, and can
be maintained even without any solvent molecules being
(aP)2 + bP]. P = (Fo2 + 2Fc2)/3
present at 100
was obtained by heating the single crystal
air atmosphere for a period of 2 h. The X-ray structure of
°
C (Fig. S1). The desolvated crystal [4-pmntd] (
2)
Results and discussion
1
at 100 C under an
°
2
Structure description of compound 1
indicates that the adjacent naphthalene ring planes
overlapped with each other by about 20%, and the
perpendicular distance between them was measured to be
approximately 3.39 Å, which corresponds to the formation of
π-π interaction between the adjacent naphthalene rings( Fig.
3). There was also no π-π interaction between the adjacent
The cocrystal composed of 4-pmntd and water was determined by
X-ray crystallographic analysis. Figure 1 shows the molecular
packing of the compound 1. The π-π interaction between the
adjacent naphthalene rings overlap with a 3.34Å interplanar
distance propagates into the direction of the b-axis and makes
stacking column structures. The pyridine ring planes of two
adjacent molecules in 1 hardly overlapped at all, so there was
pyridine rings. In
2, four 4-pmntd molecules are hydrogen
bonded via O(-C=O) atom
…pyridine H bonding to form a
rectangular grid of 9.1×3.7 Å voids in the ac-plane, and the
naphthalene rings of adjacent layers stack to make empty
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channels along the b-axis.To study the host-guest interactions
of pyridine-base H-bond, brief immersion of single crystal
into water results in complete rehydration and formation of
hydrated crystal [4-pmntd·2H2O]( ), including two guest water
molecules. The single-crystal X-ray structure determination of
revealed that hydrogen bonded water molecules reside in
the tubular framework of the 4-pmntd host connected via
water molecules and water…pyridine bonding (Ow1-
Fig. 5 The 2D network through π-π interaction of compound 3.
2
Structural diversity
It is generally believed that most organic crystals tend to collapse as
the guest solvent molecules being removed for the magnitude of
local stress depends on the organic host frameworks. In the present
crystals 1-3, the difference between the 1 and 2 is rather small, only
the distance of adjacent naphthalene ring planes expanding 0.04 Å,
so the crystal can preserve the three-dimensional order by small
adjustments in the unit cell. The adjacent naphthalene rings’
interaction is considered to play an important role as buffer
stacking layers in the crystal, in which π-π interaction absorb the
strain energy by adjusting their intermolecular distances and keep
the crystal packing stable even after large deformation.20 when 2 is
immersed in water, the water molecules filled the empty channels
of 2, hydrogen bonded water molecules reside in the tubular
framework of the 4-pmntd host connected via water molecules and
water…pyridine H bonding (Ow1-Hc…Ow1 2.83 Å, Ow1-Hb…N1 2.89
Å), which stabilized the organic host framework, so 2 converted to
the two-hydrate form 1. Single crystals 2 expose to air for seven
days, for the magnitude of local stress, the frameworks contraction
and adjacent pyridine rings get close to each other, form a strong π-
π interaction, result in formation a zigzag chain close arrangement
structure 3.
1
1
H
Hc…Ow1 2.83 Å, Ow1-Hb…N1 2.89 Å). The π-π interaction
between the adjacent naphthalene rings overlap with a 3.35Å
interplanar distance and the adjacent pyridine rings has no π-π
interaction. Interestingly, a single crystal
2 exposed to air for
seven days changed its shape and shrank of about 8%(Fig. S2).
Single crystal X-ray diffraction showed that it is a new
anhydrous crystalline form [4-pmntd](3) exhibiting a zigzag
chain arrangement of molecules via pyridine rings π-π
interaction. A strong π-π interaction occurs among adjacent
pyridine planes, which are overlapped almost face-to-face with
a distance between them of approximately 3.71 Å (Fig. 4);
however, there is also weak π-π interaction between the
adjacent naphthalene rings with a distance of approximately
4.16 Å and overlapped with each other by about 10%. Thus a
2D network is formed through π-π interaction. 19
Fig. 3 The void framework of compound
guest molecules.
2 up on removal of
Fig. 4 The dense packing of compound 3.
4 | J. Name., 2012, 00, 1-3
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Fig. 6 Reversible single-crystal-to-single-crystal transformations
between 1, 2 and 3.
desorption curve did not trace the adsorption curve any longer,
which has large hysteresis. According to the interesting
a
phenomenon, we deduced that one water molecule is firstly
adsorbed in the H bonding pyridine nitrogen sites, the secondly 1
molecule of water fast enter the channels through H bonding
interaction between water molecules, and thirdly 6 molecules of
water are adsorbed in the channels. The water molecules strongly
interact with the organic host framework through H bonding
interaction, and therefore, desorption becomes difficult and shows
a hysteresis profile. The water adsorption of 2 has dynamic
adsorption property wherein the organic host framework was
changed according to the guest molecules entering. The methanol
(kinetic diameter = 3.6 Å) vapor adsorption curve shows that after
an initial adsorption with about a molecule of methanol at
P/P0<0.45 per unit pore, another molecule of methanol adsorption
occurred at 0.45 < P/P0 <1.0. In the case of MeOH, one methanol
molecule could be firstly adsorbed in the pyridine nitrogen sites and
the following molecules of methanol are adsorbed in channels’
surface by H-bonding interactions with the pyridine groups of the
ligand, which results in a two stepwise adsorption profile. The
stepwise sorption curves of 2 for water and methanol show a
hysteretic sorption behavior correlating with the diversity of the
binding sites. However, the absorption experiments with ethanol, n-
propanol, isopropanol, n-butanol, benzene (5.3 Å) at 298 K show
these molecules cannot enter the channels of 2 for the large size.
The selective sorption of water over methanol, ethanol, n-propanol,
isopropanol, n-butanol, benzene in 2 is due both to a size effect,
which helps smaller guest molecules to enter the channels, and to
selective H-binds within the hydrophilic channels, which favours
alcohol solvents (Fig. 8).
Thermal stability
The stepwise thermogravimetric curve of 1 indicates that the
release of the guest water molecules occurred at the range from 60
to 120
360
accomplished by heating at the temperature range between 120
and 360 . On further heating, the compound decomposes to form
unidentified products (Fig. S3). The water release occurs stepwise in
the range of 70 to 120 , the first step is from 70 to 100 and
, as it is pointed out also
°C
, and give the desolvated form, 2, which is stable up to
°C (calcd 7.4%; found 7.8%). Therefore, the desolvation can be
°C
℃
℃
℃
the second step is from 100
℃ to 120℃
by DSC. (Fig. S4).
Sorption properties of 2
To study the effect of structural transformation and verify the
porosity of 2, the gas sorption properties were measured for N2
(kinetic diameter = 3.64 Å), H2 (2.8 Å), and CO2 (3.3 Å) gases. All
adsorption isotherms of 2 show type І behavior as expected for
materials with micropores (~5 Å). (Fig. 7). Interestingly, 2 can
absorb an amount of CO2 at 1 atm and 195 K [21.8 cm3 g-1 (STP)],
exhibiting highly selective sorption of CO2 over N2 [2.4 cm3 g-1 (STP)]
and H2 [2.6 cm3 g-1 (STP)]. It was also observed that there is some
sort of hysteresis between CO2 sorption/desorption curves, which
might originate from the strong interactions of CO2 molecules with
the host solid 2 and/or a dynamic structural transformation from
desolvated to guest occupied structure. The different adsorption
capabilities for gases can be ascribed to the existence of a larger
quadrupolar moment for CO2 (quadrupolar moment = 4.30 × 1026
esu cm2) than N2 (1.52 × 1026 esu cm2) and H2 (0.662 × 1026 esu cm2),
thereby providing stronger framework-partial-charge/quadrupole
interactions for CO2.12 We reasoned that the pyridine nitrogen atom
of the organic components in 2 also might enhance the selectivity
for adsorbed CO2 molecules.
50
45
N2 at 77K
H2 at 77K
40
35
30
25
20
15
10
5
CO2 at 195K
Sorption experiments with different solvents were also carried out
at 298 K (Fig. 8). For water vapor adsorption, an increase in the
amount of adsorbed vapor under low pressure (0 < P/P0 < 0.13)
indicates initial adsorption of 1 molecule of water per 4-pmntd
molecule unit, and then at 0.13 < P/P0 < 0.14, a rapid increase of
adsorption with 1 molecules of water per 4-pmntd molecule unit,
and the third stepwise sorption at 0.14 < P/P0 < 1.0 is an adsorption
with 6 molecules of water per unit pore. It was found that the
0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
p/p0
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Fig.7 Gas adsorption/desorption isotherms of 2
chromophores.14a Therefore, the powder fluorescence emission of
4-pmntd in the aggregate solid state could be changed by altering
its molecular stacking mode. 14b The supramolecular fluorescence
host system 2 might be expected to exhibit solvent water
water
methanol
400
ethanol
n-propanol
350
isopropanol
n-butanol
benzene
dependent solid state fluorescence properties. Dispersing 2 in 2 mL
of water weakened the luminescence, as molecules of 4-pmntd
aggregate as in the hydrate crystal form 1 (Fig. S7); dispersing 2 in 2
mL of MeOH, EtOH, CH3CN, THF, acetone and benzene solvent
enhanced the luminescence, 4-pmntd molecules aggregate to give
an amorphous state (Fig. S8). Interestingly, the emission intensity of
compound 2 decreased dispersing in 2 mL of water. To further
understand this phenomenon, the same experiments were
performed with the introduction of methanol, ethanol, acetnitrile,
acetone, tetrahydrofuran and benzene (Figure 10). When
300
250
200
150
100
50
0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
p/p0
Fig. 8 Different solvents vapor adsorption/desorption isotherm at
compound 2 is dispersed in 2 mL of these solvents, the fluorescence
intensity increased, that is different from the effect of adding water
solvent. We speculate that the variation arises because water
molecules can enter the small channels, leading to strongly H-
bonding interactions between pyridine and water molecules, which
decreased fluorescence intensity. We have discovered a novel
example of naphthalene diimide fluorescence in the molecule 4-
pmntd, which exhibits distinctly different fluorescence emission in
its three crystals. It was found that water molecule H-bonds and π-π
interaction between the neighbouring molecules weakened or
induced the shift in fluorescence emission. This fluorescence
switchable feature of 4-pmntd may have potential for application in
298 K for 2
Fluorescence property
The fluorescence emission spectra of the 4-pmntd in chloroform
solution shows an intense emission band at 440nm with a shoulder
around 412 nm upon excitation at 360nm (Fig. S5). With increasing
concentration of the 4-pmntd solution, the intensity of the short-
wavelength emission gradually enhances and becomes dominant.
The UV–visible absorption spectra of the compound 3 in solid-state
is shown in Fig.S6. The absorption band 360 nm is attributed to the
π– π* transition absorption of aromatic ring. The normalized solid-
state fluorescence spectra of compounds 1-3 are shown in Fig. 9.
The intensity of this fluorescence was found to vary much from that
of the solid-state sample. The presence of water molecules for 1
weakened the solid-state fluorescence intensity of 4-pmntd, each
hydrogen-bonded dimer unit is held together by the π-π stacking
interaction of naphthalene rings. It is well known that the π-π
stacking of planar molecules may facilitate the formation of
detrimental excimeric species and lead to fluorescence quenching
in the solid-state.21 Powderd 2 shows solid-state luminescence at
475nm, 540nm which undergoes a red shift to 480nm, 550nm in the
3. The pyridine planes of two adjacent molecules in 2 hardly
overlapped at all, there was nearly no π-π interaction in 2, but there
was a strong π-π interaction between the adjacent pyridine planes
overlapped almost in a face-to-face stack, so the increase in exciton
coupling and orbital overlap between neighbouring molecules from
2 to 3 is an important factor for the red-shifted fluorescence,
increased exciton coupling and orbital overlap could lead to a
strong red shift of the emission of the lowest state of the coupled
water-sensing materials.
450
400
1
2
350
3
300
250
200
150
100
50
0
400
450
500
550
600
650
700
wavelength/nm
Fig. 9 solid-state luminescence ( λex=365nm) of compounds 1-3
6 | J. Name., 2012, 00, 1-3
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136, 547
600
500
400
300
200
100
blank
water
methanol
ethanol
acetonitrile
acetone
4
5
6
tetrahydrofuran
benzene
0
400
450
500
550
600
650
700
wavelength/nm
7
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8
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Conclusions
In summary, the supramolecular organic structure shrank and
expanded induced by temperature that exhibits outstanding
performance as selective adsorption of CO2 over N2, H2. The
supramolecular organic structure shows a sorption selectivity
for water over methanol, ethanol, n-propanol, isopropanol, n-
butanol, benzene guests owing to the effect of shape exclusion.
Notably, this feature of obvious fluorescence quenching
induced by the presence of water is highly promising for
detecting water molecules through a simple fluorescence
sensing mechanism.
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This work was financially supported by the National Natural
Science Foundation of China (No.21403191), the Natural
Science Foundation of Guangdong Province (No.
2014A030307010), Special funds for public welfare research
and capacity building in Guangdong Province (No.
2015A010105031 and 2016A010103042).
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Abstract Graphical
Supramolecular structural transformation of N, N´-bis(4-pyridyl
-methyl)-naphthalene diimide and fluorescence sensing water
ab
c
Guo-Bi Li, Qing-Yuan Yang, Rong-Kai Pan, a Sheng-Gui Liu,*a
Yao-Wei Xu* b
Temperature induced phase transitions in a supramolecular
structure. The supramolecular organic structure exhibits
reversible dehydration/rehydration in a single-crystal-to-single-
crystal process and selectively adsorption of CO2 over N2, H2.
Moreover, The supramolecular organic structure shows
sorption selectivity for water and fluorescence sensing water.
a
8 | J. Name., 2012, 00, 1-3
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