Alkyl Chain Length-Selective Vapor-Induced Fluorochromism of Pillar[5]arene-Based Nonporous Adaptive Crystals

Article abstract of DOI:10.1021/jacs.9b05054

Developing new vapochromic fluorescent sensing materials with selectivity is in great demand due to serious air pollution caused by volatile organic compounds. Here we report the first nonporous adaptive crystals with vapor-induced fluorochromism. The emission of anthracene conjugated pillar[5]arene P5en crystals blue shifts from bright yellow to green upon exposure to vapors of linear alkyl ketones with alkyl chain length selectivity. Powder and single crystal X-ray diffraction analyses reveal the relationship between vapor-induced crystal structural transformation and fluorochromism. After exposure to 2-butanone, 2-pentanone, and 2-hexanone, the anthracene groups in P5en exist as monomers in the solid state, while after exposure to heptanone and octanone, the anthracene groups instead aggregate as excimers in the solid state. By solid-state NMR and thermogravimetric analysis, we further find that the size fit between ketone molecules and interspaces in P5en crystals lead to the alkyl chain length selectivity. This work provides a new strategy to design vapochromic fluorescent crystalline materials and crystalline transformation systems.

Full text of DOI:10.1021/jacs.9b05054

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Communication
Alkyl Chain Length-Selective Vapor-Induced Fluorochromism
of Pillar[5]arene-Based Nonporous Adaptive Crystals
Qi Li, Huangtianzhi Zhu, and Feihe Huang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b05054 • Publication Date (Web): 12 Aug 2019
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Alkyl Chain Length-Selective Vapor-Induced Fluorochromism
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of Pillar[5]arene-Based Nonporous Adaptive Crystals
Qi Li, Huangtianzhi Zhu, and Feihe Huang*
State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance & Novel Materials, Department of Chemistry,
Zhejiang University, Hangzhou 310027, P. R. China
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drawing a lot of attention and have shown extraordinary talents
ABSTRACT: Developing new vapochromic fluorescent
for various applications.7 Taking advantages of their regular
sensing materials with selectivity is in great demand due to
skeleton structure and host cavities, they were used in the
serious air pollution caused by volatile organic compounds
construction of porous or framework materials for adsorption and
(VOCs). Here we report the first nonporous adaptive crystals
separation of gases and organic compounds.8 Recently,
(NACs) with vapor-induced fluorochromism. The emission of
pillararene-based nonporous adaptive crystals (NACs) were
anthracene conjugated pillar[5]arene P5en crystals blue shifts
exploited in adsorption and separation of vapors and showed good
from bright yellow to green upon exposure to vapors of linear
performance.9
alkyl ketones with alkyl chain length selectivity. Powder and
single crystal X-ray diffraction analyses reveal the relationship
between vapor-induced crystal transformation and
Scheme 1. (a) Chemical structure and single crystal structure of
P5en. Solvent molecules and hydrogen atoms are omitted for
clarity. Carbon atoms are gray, oxygen atoms are red and alkyne
groups are blue. (b) Chemical structures of ketones with different
lengths of alkyl chains. (c) Representation of activation and
vapochromic processes of P5en crystals. Insert: photographs of
P5en crystals exposed to different ketones taken under sunlight
(upper) and 365 nm UV light (lower).
fluorochromism. After exposure to C4 to C6 ketones, the
anthracene groups in P5en exist as monomers in the solid state,
while after exposure to heptanone and octanone, the
anthracene groups instead aggregate as excimers in the solid
state. By solid-state NMR and thermogravimetric analysis, we
further find that the size fit between ketone molecules and
interspaces in P5en crystals lead to the alkyl chain length
selectivity. This work provides a new strategy to design
vapochromic fluorescent crystalline materials and crystalline
transformation systems.
Tuning and controlling photophysical properties of solid
materials with stimuli-responsiveness has been ardently studied in
both fundamental research and practical applications in the fields
of sensing, memories, data-security and display devices.1 In most
reported cases, the stimuli-induced twist or rearrangement of
molecules was proved to cause changes of color/emission by
modulating the molecular electronic structures and weak
intermolecular interactions such as hydrogen bonding,
metal-metal interactions, π-π interactions, etc.2 Vapochromic
materials, which quickly and selectively respond to certain
gaseous or volatile organic compounds (VOCs), are seen as
appealing candidates for applications in environmental
management and industrial production monitoring.3 Over the
years, small organic molecules, polymers, coordination complexes,
metal organic frameworks (MOFs), and covalent organic
frameworks (COFs) have all been employed as vapochromic
materials.4 However, the difficulties of molecular design &
sythesis, the limits of stability and reversibility/recyclability, and
sometimes high cost and high toxicity bring troubles to
researchers. What’s more, fluorescence sensing materials
demonstrate stronger capacity for precise and in situ analyses due
to their high sensitivity, fast response time, and high reliability.5
Therefore, the development of new vapochromic fluorescent
sensing materials owning advantages of high sensitivity, synthetic
simplicity, low cost, durability, recyclability and eco-friendliness
is in great demand so that vapochromic materials can be applied
more widely as chemical sensors and monitors.
Inspired by the good performance of NACs in adsorption and
separation of vapors, we supposed that NACs had potential to be a
new type of vapochromic material with the following features.
First, pillararene crystals tend to adsorb and capture certain
gaseous molecules, accompanied by crystal structure
transformations, which coincide with vapochromism. Second,
intrinsic cavities of pillararenes provide channels for specific
guest vapor molecules to enter and move inside the crystals,
which
guarantees
selective
response
and
structural
transformations. Third, facile functionalization of pillararenes
endows NACs with various moieties that can be tailored for target
properties and applications. Fourth, the good stability and
recyclability of NACs can decrease the cost of using NACs as
vapochromic materials.9
Up to now, only NACs based on pillar[4]arene[1]quinone
exhibited color changes with different solvent vapors.10
Vapor-induced fluorochromic NACs haven’t been studied yet.
Here we report the use of an anthracene-containing pillar[5]arene
(P5en, Scheme 1) to prepare the first NACs with vapor-induced
Macrocyclic hosts, which can selectively capture guest
molecules via host−guest interactions, have been explored for
decades and are playing significant roles in different fields.6 As a
young member, with a unique pillar structure, pillararenes are
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fluorochromism. Due to the conjugated anthracene moieties, P5en
fluorescence colors before and after adsorption. To measure the
color change under visble light, we used diffuse reflectance
spectrometry to analyze the reflectance and ploted the data on a
CIE chromaticity diagram (Figure 1c and 1d). The color of the
powder under visible light had a small change from yellow to
yellow-green after exposure to C4-C6 vapors. These phenomena
indicated the vapor-induced fluorochromism.
shows vapochromic behavior with selectivity to the length of
alkyl chains so that only the vapors of linear ketones containing
4−6 carbon atoms (denoted as C4 to C6) are able to trigger the
fluorescence change. Moreover, after removing these ketone
molecules from the crystals, the fluorescences of the crystals
revert to their initial states (Scheme 1).
The optical properties of crystalline materials are closely
connected to their crystal structures. To understand the
mechanism of vapor-induced fluorochromism, we obtained single
crystals of P5en-C3, P5en-C4, P5en-C5 and P5en-C6 by
dissolving P5en in these ketones and evaporating the solutions at
room temperature. X-ray diffraction data (Table S1) revealed that
the P5en-C3 single crystal structure belonged to the orthorhombic
crystal system and Pbca space group, while P5en-C4, P5en-C5
and P5en-C6 single crystal structures belonged to the monoclinic
crystal system and P21/n space group. In these crystals, the
molecular conformations of P5en were similar but the stacking
modes of anthracene units in two types of crystal stuctures were
different. In the P5en-C3 single crystal structures (Figure 2a), a
pair of P5en molecules were in face-to-face position with a short
distance (~3.38 Å) between anthracene units, demonstrating
strong π-π interaction and the formation of an H-aggregated
anthracene excimer, whose emission was red-shifted. However,
the analysis of other three single crystal structures (P5en-C4 in
Figure 2b, P5en-C5 and P5en-C6 in Figure S9) revealed that the
P5en couples were staggered apart because the the ketone
molecules occupied the spaces between P5en molecules.
Consequently, the anthracene excimers disassembled into
J-aggregated monomers resulting in a blue-shifed green emission.
After we knew the mechanism of different fluorescences, we
had to figure out whether the adsorption of ketone vapors was
capable of changing the structures of P5en powders. Powder
X-ray diffraction (PXRD) experiments were carried out to
characterize the P5en powders after exposure to C4-C8 vapors
(physically adsorbed ketone molecules on the surfaces of crystal
powders were eliminated by heating at 40 °C in vacuum). As
shown in Figure 2c, PXRD partterns of P5en-C4, P5en-C5 and
P5en-C6 powders were different from that of P5en-C3 powder,
which confirmed crystal structure transformation after uptakes of
C4-C6 vapor molecules. These PXRD patterns were accurately
consistent with simulated patterns from their single crystal
structures, verifying the match between the structures of the
powders and the corresponding single crystal structures (Figure
S10). On the contrary, uptake of C7 and C8 vapor didn’t alter the
structure of P5en powders, evidenced by negligible changes of
PXRD partterns before and after adsorption. Single crystal and
PXRD analysis provided significant evidences to explain the
vapor-induced fluorochromic behavior: excimers of anthracene
units in the initial P5en crystals transformed to monomers after
adsorption of C4-C6 vapors and caused an emission change, while
C7 and C8 vapors weren’t able to alter the aggregation mode of
anthracene units.
The fluorescent pillararene P5en was synthesized through a
Sonogashira coupling reaction from methoxy-pillar[5]arene with a
pair of triflate groups, and well characterized by 1H and 13C NMR
spectroscopy (Figures S4 and S5). After evaporating a saturated
solution of P5en in acetone, yellow crystals (P5en-C3) with
bright yellow fluorescence were obtained. The single crystal
structure of P5en is shown in Scheme 1a, and a near-planar
conjugated moiety was observed, which endowed the crystal with
strong fluorescence. Besides, the cavity of P5en and the spaces
between P5en molecules were filled with acetone molecules.
Thus before we tested its vapor-induced fluorochromic behavior,
we smashed P5en-C3 crystals to powder and heated it to 120 °C
in vacuum overnight to remove acetone molecules and activate it.
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Figure 1. (a) Normalized fluorescence spectra and (b)
fluorescence CIE chromaticity diagram of P5en crystal powders
before and after adsorption of linear alkyl ketones (λex = 405 nm).
(c) Diffuse reflectance spectra and (d) CIE chromaticity diagram
of P5en powders before and after adsorption of linear alkyl
ketones.
The activated powder was subsequently exposed to various
selected organic vapors and specially displayed a fluorescence
change from yellow to green under butanone (C4) vapor (Figure
S8). More interestingly, as the alkyl chain grew, P5en crystals
gave different responses to a series of linear alkyl ketones. As
shown in solid-state fluorescence spectra (Figure 1a), exposing
activated powder to C4, C5 and C6 induced distinct blue shifts of
the fluorescence, whereas vapors of C7 and C8 didn’t cause any
fluorescence change. The CIE chromaticity diagram (Figure 1b)
corresponding to fluorescence spectra demonstrated different
To further understand why C7 or C8 didn’t trigger crystal
transformations or fluorescence changes, firstly we used
solid-state 13C NMR to determine whether C7 or C8 could be
adsorbed by P5en powders. After removing physically adsorbed
ketone molecules on the surfaces, these samples were analyzed
and the data are shown in Figure 3a.
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Figure 2. (a) Arrangement (left) and a pair (right, showing excimer-type aggregation of anthracene groups) of P5en molecules in the
P5en-C3 single crystal structure. (b) Arrangement (left) and a pair (right, showing monomer-type aggregation of anthracene groups) of
P5en molecules in the P5en-C4 single crystal structure. (c) Powder X-ray diffraction patterns of P5en powders before (I) and after uptake
of (II) C3, (III) C4, (IV) C5, (V) C6, (VI) C7 and (VII) C8.
vapor molecules, and these results were consistent with their
single crystal structures with ketone molecules both in the cavity
of P5en and in the interspaces between P5en molecules. However,
TGA curves of powders exposed to C7 or C8 indicated that one
P5en molecule only adsorbed one ketone molecule, and thus near
1:1 adsorption of C7 and C8 by P5en powders was verified. We
presumed that C7 and C8 molecules were restricted in cavities of
P5en molecules rather than occupying the spaces between P5en
molecules due to their large molecular volume, which preserved
the integrity of the anthracene excimers and maintained the
yellow fluorescence. To verify if other ketones, in which the
carbonyl group is not in the penultimate position, would interfere
with the selectivity, we tested the vapochromic behavior of P5en
after exposure to 3-pentanone, 3-hexanone, 3-heptanone,
4-heptanone and 3-octanone. The results showed that the
selectivity of P5en to ketones wasn’t affected by the position of
Figure 3. (a) Solid-state 13C NMR spectra of activated P5en
the carbonyl group (Figure S12).
crystals before (top) and after uptake of ketone vapors. The peaks
referred to ketone molecules are marked with dots. TGA curves of
P5en crystals after uptake of (b) C4 and (c) C7. The weight loss
of activated P5en crystals is shown in the gray dashed line. The
numbers of ketone molecules adsorbed by one P5en molecule are
given. All crystals were heated at 40 °C for 30 min in vacuum to
remove physically adsorbed ketone molecules on the surfaces.
From the spectra, the signals belonging to ketones with
considerable strengthes were clearly identified, which confirmed
the adsorption of ketones, especially C7 and C8, by P5en powders.
Furthermore, thermogravimetric analysis (TGA) was carried out
to quantitively determine the amount of adsorbed ketone. As
shown in Figures 3b, 3c and S11, the dashed line refers to the
weight loss of activated P5en powders, which exhibited negligible
weight loss before decomposition. Upon uptakes of C4-C6, one
P5en molecule adsorbed more than two ketone molecules on
average, calculated from the weigh loss (solid line) by releasing
Figure 4. (a) Fluorescence changes of P5en-C4 powders in five
cycles. (b) The molecular ratio between absorbed C4 and P5en
measured by TGA of each cycle.
Thereafter, we tested the recyclability of the vapor-induced
fluorochromism. Like previous NACs, P5en could be easily
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4793−4802; (b) Bai, L.; Jana, A.; Tham, H. P.; Nguyen, K. T.; Borah,
recycled by simply heating the ketone-containing powders in
vacuum: green-emissive crystals consisting of anthracene
monomers returned to yellow-emissive crystals consisting of
anthracene excimers after eliminating ketone molecules (Figure
S13), and these crystals were capable of being used for several
cycles (Figure 4).
In summary, we designed and sythesized anthracene conjugated
pillar[5]arene P5en and used it to prepare the first NACs with
vapor-induced fluorochromism. P5en showed vapochromic
fluroescence to ketone vapors with alkyl length selectivity. Single
crystal analysis revealed that different aggregation modes of
anthracene units were the main reason for different emissions.
Furthermore, according to solid-state 13C NMR spectra and TGA
curves, we found that C3-C8 vapors could be absorbed by P5en
crystals but in different amounts. Additionally, the vapor-induced
fluorochromism exhibited good reversibility. This work shows the
applicational potentials of NACs for VOC detection and sensing.
P.; Zhao, Y. Remarkable Vapochromic Behavior of Pure Organic
Octahedron Embedded in Porous Frameworks. Small 2016, 12,
3302−3308; (c) Zhang, Z.; Chen, Q. Vapochromic Behavior of MOF
for Selective Sensing of Ethanol. Spectrochim. Acta A 2018, 194,
158−162.
5. Lee, M. H.; Kim, J. S.; Sessler, J. L. Small Molecule-Based
Ratiometric Fluorescence Probes for Cations, Anions, and
Biomolecules. Chem. Soc. Rev. 2015, 44, 4185−4191.
6. (a) Ma, X.; Tian, H. Bright Functional Rotaxanes. Chem. Soc. Rev.
2010, 39, 70−80; (b) Guo, D.-S.; Liu, Y. Calixarene-Based
Supramolecular Polymerization in Solution. Chem. Soc. Rev. 2012, 41,
5907−5921; (c) Han, Y.; Tian, Y.; Li, Z.; Wang, F.
Donor-Acceptor-Type Supramolecular Polymers on the Basis of
Preorganized Molecular Tweezers/Guest Complexation. Chem. Soc.
Rev. 2018, 47, 5165−5176; (d) Jana, A.; Bähring, S.; Ishida, M.;
Goeb, S.; Canevet, D.; Sallé, M.; Jeppesen, J. O.; Sessler, J. L.
Functionalised Tetrathiafulvalene- (TTF-) Macrocycles: Recent
Trends in Applied Supramolecular Chemistry. Chem. Soc. Rev. 2018,
47, 5614−5645
7. (a) Ogoshi, T.; Kanai, S.; Fujinami, S.; Yamagishi, T.; Nakamoto,Y.
para-Bridged Symmetrical Pillar[5]arenes: Their Lewis Acid
Catalyzed Synthesis and Host–Guest Property. J. Am. Chem. Soc.
2008, 130, 5022−5023; (b) Si, W.; Chen, L.; Hu, X.-B.; Tang, G.;
Chen, Z.; Hou, J.-L.; Li, Z.-T. Selective Artificial Transmembrane
Channels for Protons by Formation of Water Wires. Angew. Chem.
Int. Ed. 2011, 50, 12564−12568; (c) Xue, M.; Yang, Y.; Chi, X.;
Zhang, Z.; Huang, F. Pillararenes, A New Class of Macrocycles for
Supramolecular Chemistry. Acc. Chem. Res. 2012, 45, 1294−1308; (d)
Zhang, H.; Ma, X.; Nguyue, K. T.; Zhao, Y. Biocompatible
Pillararene-Assembly-Based Carriers for Dual Bioimaging. ACS
Nano. 2013, 7, 7853−7863; (e) Li, C. Pillararene-Based
Supramolecular Polymers: from Molecular Recognition to Polymeric
Aggregates. Chem. Commun. 2014, 50, 12420−12433; (f) Shi, B.; Jie,
K.; Zhou, Y.; Zhou, J.; Xia, D.; Huang, F. Nanoparticles with
Near-Infrared Emission Enhanced by Pillararene-Based Molecular
Recognition in Water. J. Am. Chem. Soc. 2016, 138, 80−83; (g)
Zhang, H.; Liu, Z.; Zhao, Y. Pillararene-Based Self-Assembled
Amphiphiles. Chem. Soc. Rev. 2018, 47, 5491−5528.
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It also provides
a new strategy to design fluorescent
supramolecular crystalline materials and crystal transformation
systems.
ASSOCIATED CONTENT
Supporting Information
Experimental details, X-ray crystallographic files (CIF) for
P5en-C3 (CCDC number: 1899589), P5en-C4 (CCDC number:
1899590), P5en-C5 (CCDC number: 1899592), P5en-C6 (CCDC
number: 1899591), NMR spectra, and other materials. These
materials are available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
fhuang@zju.edu.cn
8. (a) Strutt, N. L.; Fairen-Jimenez, D.; Lehl, J.; Lalonde, M. B.; Snurr,
Notes
R. Q.; Farha, O. K.; Hupp, J. T.; Stoddart, J. F. Incorporation of an
The authors declare no competing financial interest.
A1/A2-Difunctionalized Pillar[5]arene into
a
Metal–Organic
Framework. J. Am. Chem. Soc. 2012, 134, 17436; (b) Talapaneni, S.
N.; Kim, D.; Barin, G.; Buyukcakir, O.; Je, S. H.; Coskun, A.
Pillar[5]arene Based Conjugated Microporous Polymers for
Propane/Methane Separation through Host–Guest Complexation.
Chem. Mater. 2016, 28, 4460−4466; (c) Tan, L.-L.; Zhu, Y. Jin, Y.;
Zhang, W.; Yang, Y.-W. Highly CO2 Selective Pillar[n]arene-Based
Supramolecular Organic Frameworks. Supramol. Chem. 2018, 30,
648−654. (d) Ogoshi, T.; Sueto, R.; Hamada, Y.; Doitomi, K.; Hirao,
H.; Sakata, Y.; Akine, S.; Kakuta, T.; Yamagishi, T. Alkane-Length
Sorting Using Activated Pillar[5]arene Crystals. Chem. Commun.,
2017, 53, 8577−8580.
ACKNOWLEDGMENT
This work was supported by the National Natural Science
Foundation of China (21434005) and the fundamental research
funds for the central universities.
REFERENCES
1. (a) Sun, H.; Liu, S.; Lin, W.; Zhang, K.; Lv, W.; Huang, X.; Huo, F.;
Yang, H.; Jenkins, G.; Zhao, Q.; Huang, W. Smart Responsive
Phosphorescent Materials for Data Recording and Security Protection.
Nat. Commun. 2014, 5, 3601; (b) Plajer, A. J.; Percástegui, E. G.;
Santella, M.; Rizzuto, F. J.; Gan, Q.; Laursen, B. W.; Nitschke, J. R.
Fluorometric Recognition of Nucleotides within a Water‐Soluble
Tetrahedral Capsule. Angew. Chem. Int. Ed. 2019, 58, 4200−4204.
2. You, L.; Zha, D.; Anslyn, E. V. Recent Advances in Supramolecular
Analytical Chemistry Using Optical Sensing. Chem. Rev. 2015, 115,
7840–7892.
9. (a) Jie, K.; Zhou, Y.; Li, E.; Huang, F. Nonporous Adaptive Crystals
of Pillararenes. Acc. Chem. Res. 2018, 51, 2064−2072; (b) Jie, K.;
Zhou, Y.; Li, E.; Zhao, R.; Huang, F. Separation of Aromatics/Cyclic
Aliphatics by Nonporous Adaptive Pillararene Crystals. Angew. Chem.
Int. Ed. 2018, 57, 12845−12849; (c) Li, E.; Zhou, Y.; Zhao, R.; Jie,
K.; Huang, F. Dihalobenzene Shape Sorting by Nonporous Adaptive
Crystals of Perbromoethylated Pillararenes. Angew. Chem. Int. Ed.
2019, 58, 3981−3985.
10. (a) Ogoshi, T.; Shimada, Y.; Sakata, Y.; Akine, S.; Yamagishi, T.
Alkane-Shape-Selective Vapochromic Behavior Based on
Crystal-State Host-Guest Complexation of Pillar[5]arene Containing
One Benzoquinone Unit. J. Am. Chem. Soc. 2017, 139, 5664−5667;
(b) Li, E.; Jie, K.; Zhou, Y.; Zhao, R.; Zhang, B.; Wang, Q.; Liu, J.;
Huang, F. Aliphatic Aldehyde Detection and Adsorption by
Nonporous Adaptive Pillar[4]arene[1]quinone Crystals with
Vapochromic Behavior. ACS Appl. Mater. Interfaces 2018, 10,
23147−23153.
3. (a) Wenger, O. S. Vapochromism in Organometallic and Coordination
Complexes: Chemical Sensors for Volatile Organic Compounds.
Chem. Rev. 2013, 113, 3686−3733; (b) Jiang, B.; Zhang, J.; Ma, J.-Q.;
Zheng, W.; Chen, L.-J.; Sun, B.; Li, C.; Hu, B.-W.; Tan, H.; Li, X.;
Yang, H.-B. Vapochromic Behavior of
a
Chair-Shaped
Supramolecular Metallacycle with Ultra-Stability. J. Am. Chem. Soc.
2016, 138, 738−741.
4. (a) Takahashi, E. Takaya, H.; Naota, T. Dynamic Vapochromic
Behaviors of Organic Crystals Based on the Open-Close Motions of
S-Shaped Donor-Acceptor Folding Units. Chem. Eur. J. 2010, 16,
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