Geminiarene: Molecular Scale Dual Selectivity for Chlorobenzene and Chlorocyclohexane Fractionation

Article abstract of DOI:10.1021/jacs.9b03559

In this work, a new version of macrocyclic arenes, namely geminiarene, has been designed and synthesized for guest complexation and chlorobenzene/chlorocyclohexane mixture separation with excellent dual selectivity. Due to its unique dual/gemini conformat

Full text of DOI:10.1021/jacs.9b03559

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Article
Geminiarene: Molecular Scale Dual Selectivity for
Chlorobenzene and Chlorocyclohexane Fractionation
Jia-Rui Wu, and Ying-Wei Yang
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 17 Jul 2019
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Geminiarene: Molecular Scale Dual Selectivity for Chlorobenzene
and Chlorocyclohexane Fractionation
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Jia-Rui Wu and Ying-Wei Yang*
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, International Joint Research Laboratory of Nano-Micro Ar-
chitecture Chemistry (NMAC), College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China
Supporting Information Placeholder
ABSTRACT: In this work, a new version of macrocyclic arenes, namely geminiarene, has been designed and synthesized for guest complexation
and chlorobenzene/chlorocyclohexane mixture separation with excellent dual selectivity. Due to its unique dual/gemini conformational feature,
not only chlorocyclohexane can be separated from chlorobenzene with exceeding 97% purity, but also chlorobenzene can be separated from
chlorocyclohexane with purity over 88%, and the dual selective fractionation process could be achieved in only one cycle of operation. Signifi-
cantly, we demonstrate that the dual selectivity capability is essentially a competition of the stability between the guest-free and guest-loaded
crystalline phases of geminiarene. We strongly believe that this work and the idea of multiple selective separation systems will open up new
perspectives on macrocycle-based solid-state host-guest chemistry and molecular scale separation materials.
itous discovery and simple fondness for macrocycle synthesis, ingen-
ious design rooted within some special vocations have become the
theme for modern synthetic macrocyclic chemistry.
INTRODUCTION
The creation and development of various molecular containers is
the core of research subject in host–guest and supramolecular chem-
istry during the past 50 years,1,2 among which, prevalent macrocyclic
It is well known that nearly all function development based on
macrocycles were carried out in solvent system, thus, macrocycle-
compounds, that is, crown ethers, cyclodextrins, calixarenes, cucur-
based solid-state host–guest chemistry investigations are always one
biturils, and pillar[n]arenes (pillarenes for short), are the most rep-
resentative examples.3 Function-directed macrocyclic derivatives
of the frontier science and hotspots, cross over many supramolecular
research fields and beyond.8 In the last few years, pillarene-based
design and synthesis endows them great contribution to different re-
molecular crystal materials have been given broad attention in virtue
search fields, including but not limited to host–guest binding, mo-
lecular machinery, extraction and separation, and biomimetics.4,5 In-
of their high selectivity, ease of preparation, nice chemical stability,
solubility, and indeed recyclability.9,10 Thus, the reality exists and
terestingly, the development of synthetic macrocycles has gradually
complicated separation problems have been successfully and ideally
transformed into an application-oriented molecular design and syn-
thesis instead of the traditional structure-directed functional estab-
lishment, and numerous examples support this view.6,7 For instance,
supramolecular organic porous crystal material, which showed high
resolved in laboratory. In 2014, we reported the first pillarene-based
selectivity and reversible adsorption toward CO2 in ambient condi-
leaning pillar[6]arene, a new version of macrocyclic arenes, was first
tion.9 Afterward, Huang, Ogoshi, Cooper et al. reported pillarene-
introduced by us in 2018, aiming at increasing the cavity flexibility
and enhancing the binding properties of traditional pillarenes.7a In
based adaptive crystal materials, where dense packing and guest-free
pillarene crystalloids were easily penetrated by preferable guest mol-
2019, Davis and coworkers reported a biomimetic macrocycle re-
ecules through solid-liquid or solid-vapor contact, achieving selec-
ceptor, which was designed and synthesized for highly selective glu-
tive guest separation and adsorption.10
cose binding.7f Hence, instead of being stuck at the stage of serendip-
Figure 1. (a) Synthetic route to geminiarene (GA). Single-crystal structures of (b) GAα and (c) GAβ obtained from different conditions.
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As a typical type of macrocycle-based material, pillarene crystals
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GA was fully characterized by NMR spectroscopy, MALDI-TOF-
MS analyses as well as X-ray single-crystal diffraction (Figures S1-S6,
Tables S1-S3), among which, two guest-free single crystals, that is,
GAα and GAβ, with completely different molecular conformations
including symmetrical characteristics, packing modes and space
groups have been first obtained (Figures 1b-c). GAα possesses a
rigid hexagon structure (Ci symmetry) (Figure 1b, right), in which
the four trimethoxybenzene units are almost perpendicular to the
plane of methylene bridges (Figure S7a) and the unsubstituted phe-
nylene rings (Figure S7b). Considering the plane established by the
methylene bridges, two adjacent trimethoxybenzene units point at
the opposite direction respectively, giving an torsion angle of ca.
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have great potentials in adsorption and separation, however, there
are still many objective challenges or limitations remained to be
solved or enhanced: (i) perethylated pillar[6]arene (EtP6A) is the
most frequently used pillarene homologue to construct crystal ma-
terials owing to its nice cavity adaptability and flexibility. However,
EtP6A usually cannot be prepared on a large scale and always accom-
panies with complicated separation and purification procedures,3f,11
thus, it may be far away from the practical use; (ii) Due to the cavity-
size limitation, 1:1 or 1:2 solid-state host–guest complexes are al-
ways observed in pillarene crystals, and strongly limit its separation
capacity and efficiency; (iii) mono-activated crystalline phase makes
the pillarene always presented single selectivity during the separa-
tion process, in other words, only one component can be separated
from a mixed system by one type of pillarene molecular crystals.10
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163° (Figure S8a), meanwhile, the two phenylene units are parallel
to each other and tilted to the same direction (Figure S8b), and all
these components leading to the regular ladder-shaped structure of
GAα with a dense packing mode (Figure 1b, left). Completely dif-
ferent from GAα, the four trimethoxybenzene units of GAβ all point
above the plane of methylene bridges, rendering a distorted bowl-
shaped structure (C2 symmetry) (Figure 1c, left). Besides, the un-
substituted phenylene units are no longer parallel with each other as
a result of the desymmetrical molecular configuration of GAβ. Inter-
estingly, each molecule in GAβ further interacts with twelve near
neighbors through multiple C-H···O and aromatic π-π interactions
(Figure S9), presenting a layer-by-layer packing modes with infinite
1D channels (Figure 1c, right). Additionally, the cavity of GAα is
about 8.5 Å in width and 4.7 Å in height, and accordingly the diam-
eter of the incircle of Gaβ is ca. 4.3 Å, which are all defined by meas-
uring the distances between the corresponding carbon atoms after
subtracting the Van der Waals radii(Figure S10).
The separation of aliphatic cyclic compounds from correspond-
ing aromatic compounds has been listed as one of the difficult sepa-
ration subjects due to their similar physical properties.12 Chloroben-
zene (CB), a chlorinated aromatic organic compound, is frequently
used as an organic solvent, starting reagent, and organic synthesis in-
termediate in chemical industry.13 However, CB can cause serious
harm to the environment and human health as a result of its strong
bioaccumulation, acute toxicity, and chemical stablility.14 Besides, to
some extent, CB also contributes to global warming and ozone de-
pletion. So, it’s necessary to convert it to alternative compounds that
are environmentally acceptable or reusable before discharge.15 By
hydrogenation or electrochemical degradation of CB, chlorocyclo-
hexane (CCH), a less harmful chlorinated aliphatic cyclic com-
pound and useful pharmaceutical intermediate, could be obtained.16
But, due to their similar boiling points (CB 132 °C，CCH 142 °C),
it is unrealistic to use the traditional separation methods, such as dis-
tillation, to separate CCH with high purity from the unreacted CB.
Here we report a new class of supramolecular macrocyclic arene,
referred to as geminiarene (GA), named by us according to its two
superficially different but actually interconvertible solid-state config-
urations (referred to as GAα and GAβ). Besides, GA combines the
virtues of low cost, ease of synthesis, high preparation yield, well-de-
fined structure, and superior crystal-state host–guest properties.
Most importantly, GA possesses the capability in dual selective mix-
ture separation as a result of its two conformational structures natu-
rally with different guest binding preferences. Taking the CB/CCH
mixture separation as an example, GA could separate CCH from CB
with more than 97% purity, while, also can separate CB from CCH
with a purity over 87%, and both the selective separation could be
realized in one single cycle, thus, molecular scale fractionation pro-
cess for CB/CCH mixture could be facilely achieved.
RESULTS AND DISCUSSION
Synthesis, structural analysis and crystal-state host–guest in-
vestigation of GA. A facile two-step synthetic approach for GA was
adopted: 1,3,5-trimethoxybenzene was reacted with 1,4-bis(chloro-
methyl)benzene catalyzed by AlCl3 in a Friedel-Crafts alkylation re-
action, giving the coupling precursor 1,4-bis(2,4,6-trimethoxyben-
zyl)benzene in a yield of 45%; then, the Bronsted acid-catalyzed
fragment coupling method by reaction of 1,4-bis(2,4,6-trimethox-
ybenzyl)benzene with excess paraformaldehyde in the presence of
trifluoroacetic acid led to the formation of GA in an excellent yield
of 85 % (Figure 1a). The best reaction time would be 30-40 min at
ambient temperature, and prolonged reaction time will increase the
yields of oligomers and polymers thus decrease the yield of GA.
Figure 2. X-ray single-crystal structures of (a) DEM⊂GA, (b) 1,4-
dioxane⊂GA, (c) 4(1,3-dioxane)⊂GA, (d) 4(THP)⊂GA. (e) TGA
and DSC studies of 1,4-dioxane⊂GA: (left) tested without natural
weathering, (right) tested after natural weathering over 1000 hrs.
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Scheme 1. Interconversion of the various GA-based single crystal structures in solution and the solid state. (a) Chemical structure of geminiarene (GA),
chlorobenzene (CB), and chlorocyclohexane (CCH). Single crystal structures of (b) 2(DCM)⊂GA, (c) GAα, (d) 4(CCH)⊂GA, (f) GAβ, (g) CB⊂GA.
(e) After heating 4(CCH)⊂GA at 30 °C for 20 min, a stable intermediate state crystalline phase, referred to as 2(CCH) ⊂GA, is obtained, as confirmed by
its PXRD pattern.
Besides GAα and GAβ, a series of crystal-state GA-based host–
guest complexes were also facilely obtained, and to our surprise, not
only the lipophilic species, such as the dichloromethane (DEM) and
1,2-dichloroethane (DCM) (Figures 2a, S11, referred to as
2(DCM)⊂GA and 2(DEM)⊂GA, but also many hydrophilic or-
ganic compounds, including but not limited to 1,4-dioxane, 1,3-di-
oxane and tetrahydropyrane (THP) (Figures 2b-d, referred to as
1,4-dioxane⊂GA, 4(1,3-dioxane)⊂GA and 4(THP)⊂GA), can be
stably hosted, which proves that this newly designed macrocyclic
arene indeed possesses a wide range of guest binding capability.
More than that, there are several bright points should be paid special
attention. First, compared to nearly all the famous phenol-aldehyde
related macrocyclic compounds, such as calixarene and pillarene,
stoichiometries of 1:1 and 1:2 are the most common host–guest
binding forms in the crystal state. However, unusual 1:4 complexes
are quite common in GA host–guest complex crystals. Second, de-
spite of various packing modes in these binding crystals, GA mole-
cules can only exist in two conformations, that is, either GAα or GAβ,
further demonstrating the dual/genimi nature of GA. Moreover,
upon analyzing the crystals of 1,4-dioxane⊂GA, 4(1,3-diox-
ane)⊂GA and 4(THP)⊂GA, we can easily figure out that slight dif-
ferences from the guest species, such as molecular polarity or the po-
sition/number of the hydrogen-bond acceptors (oxygen atom), can
induce the inversion of the two conformations, that is, the crystal
polymorphs of GA are interconvertible and guest stimuli-responsive.
Additionally, 1,4-dioxane, a frequently used organic solvent and
also a common byproduct in chemical and cosmetic industry, has
been listed among the possible carcinogenic chemicals (Group 2B)
by the International Agency for Research on Cancer,17 and it cannot
be absorbed or degraded by soil due to its high hydrophilicity. So,
1,4-dioxane must be rationally used and carefully stored. According
to the thermogravimetric (TG) and differential scanning calorime-
try (DSC) measurements of 1,4-dioxane⊂GA (Figures 2e, left), 1,4-
dioxane molecules are highly stably hosted, and its release from 1,4-
dioxane⊂GA (weight loss) started at ca. 180 °C, which is approxi-
mately 80 °C higher than its boiling point (101 °C). Most im-
portantly, the molecular crystals of 1,4-dioxane⊂GA possess excel-
lent weathering resistance capability, as depicted in Figures 2e and
S12-14, no obvious loss of the trapped 1,4-dioxane molecules and
crystalline phase transformation of GA were found even after weath-
ering the binding crystalloids over 1000 hours at room temperature
in an open cell vial with air flow, which suggests that GA has great
potentials in the adsorption, purification, and especially highly stable
storage of 1,4-dioxane.
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Figure 3. (a) Time-dependent GAα solid–liquid sorption plot for CCH/CB mixture solution at room temperature. Any surface adsorbed
CCH/CB molecules and unstably complexed CCH molecules were removed by heating the absorbed crystal samples at 30 °C for 20 min.
(b) PXRD patterns of GA: (I) original GAα; after adsorption of CCH/CB mixture solution for (II) 1 h, (III) 3 h, and (IV) 5 h; (V) simulated
PXRD pattern from single-crystal structure of 4(CCH)⊂GA. (c) Relative amounts of CCH and CB adsorbed in GAα after 5 hours by gas
chromatography. (d) Maximum uptake amount of CCH and CB in GAα after the same material is recycled five times. (e) Time-dependent
GAβ solid–vapor sorption plot for CCH/CB mixture vapor at room temperature. Any surface adsorbed CCH/CB molecules were removed
by heating the absorbed crystal samples at 30°C for 20 min. (f) PXRD patterns of GA: (I) original GAβ; (II) after adsorption of CCH vapor;
(III) after adsorption of CB vapor; (IV) after adsorption of CCH/CB mixture vapor; (V) simulated PXRD pattern from single-crystal structure
of CB⊂GA. (g) Relative amounts of CCH and CB adsorbed in GAβ after 13 hours by gas chromatography. (h) Maximum uptake amounts
of CCH and CB in GAβ after the same material is recycled five times.
CB/CCH separation by GAα. Owing to the outstanding solid-
state host–guest properties of GA, we envisioned that GAα pos-
sesses the capability of discriminating and selectively separating/ab-
sorbing CB/CCH mixture (1:1 v/v was always used) as aforemen-
tioned. Activated guest-free GAα crystals could be obtained by
desolvating the host–guest binding crystals of 2(DCM)⊂GA
(Scheme 1b-c, Figures S15-S16), which was grown by evaporation
of a CH2Cl2/CH3OH solution of GA (see Supporting Information),
and the powder X-ray diffraction (PXRD) pattern of the activated
crystalline solids was fully in line with the simulated PXRD pattern
of the guest-free GAα crystals, hence, the structure of the desolvated
crystalline phase was proved (Figure S17).
PXRD pattern presents a continuous crystal-to-crystal transfor-
mation from GAα to 4(CCH)⊂GA over 5 hours (Figure 3b), fur-
ther confirming that the mechanism of the selective adsorption is in-
deed a phase transformation process induced by preferable guests,
and as for GAα, the winner is CCH.
In order to obtain CCH with a higher purity, any CB or CCH mol-
ecules attached to the surface of the crystalloids should be removed.
Interestingly, after heating the adsorbed GAα (4(CCH)⊂GA) at
30 °C for 20 min, a stable intermediate state crystalline phase, where
CCH forms a 1:2 host–guest complex with GA was obtained (re-
ferred to as 2(CCH)⊂GA, Scheme 1e, Figure S21), and then CCH
could be released from 2(CCH)⊂GA with a purity about 98.0%
(Figures 3c, S22). The stability of the two crystalline phases were
verified by TG experiments, and compared to the release tempera-
ture of 4(CCH)⊂GA below 50 °C (Figure S23), hardly any weight
loss of 2(CCH)⊂GA was seen until the crystals were heated to 90 °C
(Figure S24). Overall, due to the relatively weak host–guest interac-
tions and extremely high separation ratio, at least half of the CCH
molecules could be facilely released from the 4(CCH)⊂GA crystals,
endowing GAα with great potentials for practical use. What’s more,
aiming to obtain the most stable data representation, time-depend-
ent solid-liquid sorption experiment by using GAα was carried out
(Figures 3a, S25). The uptake of CCH increased rapidly in a form of
nearly constant speed before reaching its saturation point (ca. 2h),
and negligible amount of CB was uptaken in the experiment. Besides,
the removal of the guest-loaded crystals, that is, 4(CCH)⊂GA and
2(CCH)⊂GA, could lead to the recovery of the original guest-free
GAα phase (Figures S26-S28), which can be further reused at least
5 times without decreasing its CCH capture performance (Figure
3d), confirming the high selectivity/efficiency/recyclability of GAα
as a new solid material for adsorption and separation.
Due to the densely-packed arrangement of GAα, hardly any CB
or CCH molecules can penetrate into the crystalloids by solid-vapor
sorption (Figures S18), not to mention the induce of a selective
loading process in a relative short time, thus, the solid-liquid direct
contact adsorption process should be considered in priority. 1H
NMR experiments revealed that GAα preferred to absorb CCH
upon immersing in a solution of CB/CCH mixture, and a high satu-
rated uptake of CCH can be identified as nearly four Mole/GA (Fig-
ure S19), on the contrary, trace amount of CB can be absorbed. Sur-
prisingly, gas chromatography (GC) experiment showed that the
purity of CCH absorbed in GAα was 97.2% (Figure S20), proving
the high selectivity of CCH in GAα. To be more confirmative, the
single crystal structure of CCH-loaded GAα was obtained (see Sup-
porting Information), in line with the adsorption test, CCH forms a
1:4 host–guest binding system with GA (referred to as
4(CCH)⊂GA, Scheme 1d, left). In this crystal structure, ladder-
shaped GA molecules help form a sandwich packing mode with infi-
nite extrinsic 2D diagonal channels, two rows of CCH molecules ac-
commodated in each interlayer, malposed and stabilized by C-H···Cl
interactions (Scheme 1d, right). Additionally, time-dependent
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Figure 4. (a) Representation of the dual selective CB/CCH fractionation by immersing activated crystals of GA in CCH/CB mixture solution at room
temperature. (b) Time-dependent GAβ solid–liquid sorption plot for CCH/CB mixture solution at room temperature. (c) Relative amount of CCH and
CB adsorbed in GAβ before (9 h, left) and after (70 h, right) the crystalline phase transformation from CB⊂GA to 4(CCH)⊂GA by gas chromatography.
(d) PXRD patterns of GA: (I) original GAβ; after adsorption of CCH/CB mixture solution for (II) 3 h and (III) 6 h; (IV) PXRD patterns of CB⊂GA; (V)
simulated PXRD pattern from single-crystal structure of CB⊂GA. (e) PXRD patterns of GA: (I) original GAβ; after adsorption of CCH/CB mixture solu-
tion for (II) 24 h, (III) 48 h and (IV) 65 h; (V) simulated PXRD pattern from single-crystal structure of 4(CCH)⊂GA.
1
CB/CCH separation by GAβ. Active GAβ could be obtained by
desolvating the GAβ crystals (Scheme 1g, Figures S29-30), which
was initially recrystallized from toluene solution (see Supporting In-
formation). As aforementioned, GAβ crystals possess a relatively
sparse packing mode (Figure 1c, right), and its intrinsic pores
prompted us to explore whether GAβ could discriminate the mix-
ture of CB and CCH through direct solid-vapor adsorption. Thus,
time-dependent solid-vapor sorption experiment by using GAβ was
carried out (Figures 3e, S31). Interestingly, the selectivity of GAβ
toward CB/CCH mixture was directly opposed to GAα, that is, the
preferable guest is CB instead of CCH in terms of GAβ crystals. Sim-
ilarly to the solid-liquid adsorption process by GAα, it took only
about five hours to complete the whole separation and adsorption
process, and a small amount of CCH was captured and proved very
stable during the whole experiment (Figure 3e). GC experiments
also confirmed a satisfactory selectivity for CB that is 88.2 % (Fig-
ures 3g, S32), meanwhile, PXRD pattern of GAβ phase transformed
after adsorption indicated that a new crystalline phase with CB-
loaded was generated (Figure 3f).
of GA (Scheme. 1g). In consistency with the H NMR and TG ex-
periments (Figures S33-S34), CB forms a 1:1 host–guest complex
with GA, and many disordered CH3OH molecules intracrystalline
1
unable to be exactly refined were further determined by H NMR,
TGA and DSC experiments (Figures S35-S37). The PXRD pattern
of GAβ after adsorption of the CB/CCH mixture vapor matched
well with the pattern after adsorption of the CB vapor, also in a good
agreement with the simulated profile from the single crystal struc-
ture of CB⊂GA (Figure 3f), which further confirming the process of
adsorption and separation is in fact the guest-triggered crystalline
phase transformation, in coordination with the relative stability of
the new formed crystal structure upon complexation. In addition, it
is worth mentioning that GAβ crystal with infinite 1D channels is
not as stable as the dense-packed GAα, and the partial intrinsic pores
could be collapsed during heating or desolvating process (Figure
S38).18 However, it still possesses the ability in discriminating and
separating the mixture vapor of CB/CCH at least 5 times without
losing its performance (Figure 3h).
Dual selective CB/CCH fractionation by GA. According to the
two completely opposite selectivity of GAα and GAβ, we wonder if
we can realize the uptake of the two compounds through only one
To rationalize this, we successfully obtained the single crystal
structure of CB⊂GA by slow evaporation of CB/CH3OH solution
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special adsorption process, that is, fractionation of the CB/CCH
the separation of CB/CCH mixture by one special macrocycle-
based crystals could be achieved.
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mixture. Therefore, time-dependent solid-liquid sorption experi-
ments using GAβ crystals were carried out (Figures 4b, S39-S41). As
expected, due to the intrinsic porosity along the a-axis, a high-speed
adsorption of CB and CCH with no obvious selectivity was observed
instantaneously, soon afterwards, the intra-crystalline CCH mole-
cules were gradually squeezed out to a minimum extend within
about 10 hours. Intriguingly, the uptake amount of CCH began to
increase rapidly after this point, and the original dominated CB mol-
ecules began to decrease and displaced by CCH. Time-dependent
PXRD patterns indicated a guest-induced continuous crystalline
phase transition from CB⊂GA to 4(CCH)⊂GA, following after
GAβ to CB⊂GA, and the whole process was completed within
about 65 hours (Figures 4d-e). Thus, a continuous and coherent
process, that is, CB molecules in the CB/CCH mixture penetrate
the GA crystals and induced the CB⊂GA formed firstly, soon after-
wards, CCH molecules trigger the configuration conversion of the
GA in CB⊂GA with the recovery of the binding ability toward CCH
in solution, leading to the new phase of 4(CCH)⊂GA generated
(Figure 4a). This suggests that the CCH-loaded 4(CCH)⊂GA is
more thermodynamically stable than CB-loaded CB⊂GA and un-
loaded GAβ crystals.
Above all, compared with other macrocycle-based crystalline sep-
aration materials, such as pillarenes, GA has several advantages.
Firstly, an efficient high yield fragment coupling process makes GA
can be prepared easily and full of potentials for mass production
upon fine-tuning of the synthetic details and separation approaches.
Secondly, up to 1:4 unusual host–guest binding forms will bring GA
with a relatively high overall guest uptake. Thirdly, multiple crystal-
line phases transformed in order by guest-inducement in solution
endows GA with dual selectivity in adsorption and separation of
CB/CCH mixture in only one cycle of operation. We strongly be-
lieve that dual or multiple separation selectivity will be one of the fu-
ture development directions of synthetic macrocycles-based crystal-
line separation materials. Discovery of triple selective separation sys-
tem based on GA and/or other novel synthetic macrocycles is still
ongoing in our laboratory.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publi-
cations website at DOI:
Chemical synthesis and characterization; Crystal structure analysis; TG,
DSC, PXRD and GC analysis; Crystallographic data for GAα
(CIF/1903737), GAβ(CIF/1903739), 2(DCM)⊂GA (CIF/1852587),
1,4-dioxane⊂GA (CIF/1903700), 4(1,3-dioxane)⊂GA (CIF/1903732),
4(THP)⊂GA (CIF/1903735), 2(DEM)⊂GA (CIF/1903730),
4(CCH)⊂GA (CIF/1903734), CB⊂GA (CIF/1903736), and all experi-
mental details (PDF).
Due to the successive phase transformation along with the loading
and displacing one after another, molecular scale dual selectivity for
CB/CCH separation can be obtained by GA molecular crystals.
Two GC experiments confirmed that the fractionation of CB before
the phase transformation is over 87% (Figure 4c, left, Figure S42),
and the fractionation of CCH after completely phase transformation
is over 97% (Figure 4c, right, Figure S43), which are all consistent
with the results of solid-liquid or solid-gas separation by GAα and
GAβ crystals as aforementioned. In other words, the CB/CCH frac-
tionation process was a result of the opposite selectivity of the two
GA crystals, in conjunction with the guest-induced configuration
conversion and phase transformations, thus, the two mixed compo-
nents could be separated orderly and effectively.
AUTHOR INFORMATION
Corresponding Author
* ywyang@jlu.edu.cn; yyang@chem.ucla.edu
Author Contributions
All authors have given approval to the final version of the manuscript.
CONCLUSIONS
In conclusion, we presented an entirely new kind of macrocyclic
arene, namely GA, which was designated according to its two totally
different, but, indeed interconvertible molecular configurations.
Taking advantage of its unique structural feature, lipophilic or hy-
drophilic species different in size, shape, and polarity could be
hosted to form 1:1, 1:2 or 1:4 solid-state host–guest assemblies. In
particular, GA presented a good binding affinity toward persistent
environmental contaminant and Group 2B carcinogen 1,4-dioxane
in the solid states, which displayed a nearly 80 °C boiling point ele-
vation and resistance to weathering erosion over 1000 hours. Most
importantly, we have investigated the CB/CCH separation by GA-
base crystalloids of GAα and GAβ. CCH can be highly purified by
GAα from an CB/CCH mixture solution through solid-liquid sorp-
tion with purity over 97%, and GAβ has the ability to separate CB
from the CB/CCH mixture vapor through solid-vapor sorption with
purity of over 88%, and both of them can be reused many times with-
out decrease in separation performance. Furthermore, we demon-
strated that GAβ and the two guest-loaded crystals (CB⊂GA and
4(CCH)⊂GA) could be transformed one after another by continu-
ous guest-induced operation. Hence, CB and CCH could be sepa-
rated consecutively in different stages of crystalline phase over time,
as a form of fractional distillation process, and the dual selectivity for
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We gratefully acknowledge the National Natural Science Foundation of
China (21871108, 51673084); Jilin Province-University Cooperative
Construction Project-Special Funds for New Materials (SXGJSF2017-
3), Jilin University Talents Cultivation Program, and the Fundamental
Research Funds for the Central Universities for financial support.
REFERENCES
1. (a) Pedersen, C. J. Cyclic Polyethers and Their Complexes with Metal
Salts. J. Am. Chem. Soc. 1967, 89, 2495; (b) Bell, T. W.; Firestone, A.
Torands: Rigid Toroidal Macrocycles. Calcium Sequestration by a Member
of This New Ligand Class. J. Am. Chem. Soc. 1986, 108, 8109; (c) Klärner,
F.-G.; Kahlert, B. Molecular Tweezers and Clips as Synthetic Receptors.
Molecular Recognition and Dynamics in Receptor−Substrate Complexes.
Acc. Chem. Res. 2003, 36, 919; (d) Kieltyka, R.; Englebienne, P.; Fakhoury,
J.; Autexier, C.; Moitessier, N.; Sleiman, H. F. A Platinum Supramolecular
Square as an Effective G-Quadruplex Binder and Telomerase Inhibitor. J.
Am. Chem. Soc. 2008, 130, 10040; (e) Hargrove, A. E.; Nieto, S.; Zhang, T.;
Sessler, J. L.; Anslyn, E. V. Artificial Receptors for the Recognition of Phos-
phorylated Molecules. Chem. Rev. 2011, 111, 6603; (f) Ma, D.; Zhang, B.;
ACS Paragon Plus Environment

Page 7 of 9
Journal of the American Chemical Society
Hoffmann, U.; Sundrup Martina, G.; Eikermann, M.; Isaacs, L. Acyclic Cu-
P. L.; Bruns, C. J.; Stern, C. L.; Sarjeant, A. A.; Stoddart, J. F. Exbox: A Poly-
cyclic Aromatic Hydrocarbon Scavenger. J. Am. Chem. Soc. 2013, 135, 183;
(c) Chun, Y.; Jiten Singh, N.; Hwang, I.-C.; Woo Lee, J.; Yu, S. U.; Kim, K.
S. Calix[n]imidazolium as a New Class of Positively Charged Homo-Calix
Compounds. Nat. Commun. 2013, 4, 1797; (d) Jia, F.; He, Z. F.; Yang, L. P.;
Pan, Z. S.; Yi, M.; Jiang, R. W.; Jiang, W. Oxatub[4]arene: A Smart Macro-
cyclic Receptor with Multiple Interconvertible Cavities. Chem. Sci. 2015, 6,
6731; (e) Huang, G. B.; Wang, S. H.; Ke, H.; Yang, L. P.; Jiang, W. Selective
Recognition of Highly Hydrophilic Molecules in Water by Endo-Function-
alized Molecular Tubes. J. Am. Chem. Soc. 2016, 138, 14550.
7. (a) Wu, J. R.; Mu, A. U.; Li, B.; Wang, C. Y.; Fang, L.; Yang, Y. W.
Desymmetrized Leaning Pillar[6]arene. Angew. Chem., Int. Ed. 2018, 57,
9853; (b) Swager, T. M.; Kim, Y. Flexible Pillar[6]arene for Enhanced
Host–Guest Properties. Synfacts 2018, 14, 0815; (c) Shetty, D.; Trabolsi, A.
Making Pillar[6]arenes to Lean: An Art of Tuning a Supramolecular Host.
Sci. China Chem. 2019, 62, 289; (d) Jia, F.; Hupatz, H.; Yang, L.-P.; Schroder,
H. V.; Li, D.-H.; Xin, S.; Lentz, D.; Witte, F.; Xie, X.; Paulus, B.; Schalley, C.
A.; Jiang, W. Naphthocage: A Flexible Yet Extremely Strong Binder for Sin-
gly Charged Organic Cations. J. Am. Chem. Soc. 2019, 141, 4468; (e) Wu, J.
R.; Yang, Y. W. New Opportunities in Synthetic Macrocyclic Arenes. Chem.
Commun. 2019, 55, 1533; (f) Tromans, R. A.; Carter, T. S.; Chabanne, L.;
Crump, M. P.; Li, H. Y.; Matlock, J. V.; Orchard, M. G.; Davis, A. P. A Bio-
mimetic Receptor for Glucose. Nat. Chem. 2019, 11, 52.
8. (a) Atwood, J. L.; Barbour, L. J.; Jerga, A. A New Type of Material for
the Recovery of Hydrogen from Gas Mixtures. Angew. Chem., Int. Ed. 2004,
43, 2948; (b) Li, T.; Fan, L.; Gong, H.; Xia, Z.; Zhu, Y.; Jiang, N.; Jiang, L.;
Liu, G.; Li, Y.; Wang, J. Janusarene: A Homoditopic Molecular Host. Angew.
Chem., Int. Ed. 2017, 56, 9473; (c) Ogoshi, T.; Shimada, Y.; Sakata, Y.; Akine,
S.; Yamagishi, T. A. 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; (d) Ogoshi, T.;
Sueto, R.; Yagyu, M.; Kojima, R.; Kakuta, T.; Yamagishi, T.; Doitomi, K.;
Tummanapelli, A. K.; Hirao, H.; Sakata, Y.; Akine, S.; Mizuno, M. Molecular
Weight Fractionation by Confinement of Polymer in One-Dimensional Pil-
lar[5]arene Channels. Nat. Commun. 2019, 10, 8; (e) Khoshkhoo, S.; Anwar,
J. Crystallization of Polymorphs: The Effect of Solvent. J. Phys. D: Appl. Phys.
1993, 26, B90; (f) Trask, A. V.; Shan, N.; Motherwell, W. D. S.; Jones, W.;
Feng, S.; Tan, R. B. H.; Carpenter, K. J. Selective Polymorph Transformation
Via Solvent-Drop Grinding. Chem. Commun. 2005, 880.
curbit[n]uril-Type Molecular Containers Bind Neuromuscular Blocking
Agents in Vitro and Reverse Neuromuscular Block in Vivo. Angew. Chem.,
Int. Ed. 2012, 51, 11358; (g) Cook, T. R.; Vajpayee, V.; Lee, M. H.; Stang, P.
J.; Chi, K.-W. Biomedical and Biochemical Applications of Self-Assembled
Metallacycles and Metallacages. Acc. Chem. Res. 2013, 46, 2464.
1
2
3
4
5
6
7
8
2. (a) Kumari, H.; Deakyne, C. A.; Atwood, J. L. Solution Structures of
Nanoassemblies Based on Pyrogallol[4]Arenes. Acc. Chem. Res. 2014, 47,
3080; (b) Chen, H. Q.; Fan, J. Z.; Hu, X. S.; Ma, J. W.; Wang, S. L.; Li, J.; Yu,
Y. H.; Jia, X. S.; Li, C. J. Biphen[n]arenes Chem. Sci. 2015, 6, 197; (c) Cook,
T. R.; Stang, P. J. Recent Developments in the Preparation and Chemistry
of Metallacycles and Metallacages Via Coordination. Chem. Rev. 2015, 115,
7001; (d) Liu, Z. C.; Nalluri, S. K. M.; Stoddart, J. F. Surveying Macrocyclic
Chemistry: From Flexible Crown Ethers to Rigid Cyclophanes. Chem. Soc.
Rev. 2017, 46, 2459; (e) Ji, X.; Wu, R.-T.; Long, L.; Guo, C.; Khashab, N. M.;
Huang, F.; Sessler, J. L. Physical Removal of Anions from Aqueous Media
by Means of a Macrocycle-Containing Polymeric Network. J. Am. Chem. Soc.
2018, 140, 2777; (f) Guerineau, V.; Rollet, M.; Viel, S.; Lepoittevin, B.;
Costa, L.; Saint-Aguet, P.; Laurent, R.; Roger, P.; Gigmes, D.; Martini, C.;
Huc, V. The Synthesis and Characterization of Giant Calixarenes. Nat. Com-
mun. 2019, 10, 14.
3. (a) Cramer, F.; Kampe, W. Inclusion Compounds. Xvii. Catalysis of
Decarboxylation by Cyclodextrins. A Model Reaction for the Mechanism of
Enzymes. J. Am. Chem. Soc. 1965, 87, 1115; (b) Pedersen, C. J. Cyclic Poly-
ethers and Their Complexes with Metal Salts. J. Am. Chem. Soc. 1967, 89,
7017; (c) Colguhoun, H. M.; Stoddart, J. F.; Williams, D. J. Coronation of
Ligating Acetonitrile by 18-Crown-6. X-Ray Crystal Structure of {[Trans-
Ir(Co) (Ch3cn)(Pph3)2]2+.18-Crown-6}[Pf6]2-.2CH2Cl2. J. Am. Chem.
Soc. 1982, 104, 1426; (d) Lagona, J.; Mukhopadhyay, P.; Chakrabarti, S.;
Isaacs, L. The Cucurbit[n]uril Family. Angew. Chem., Int. Ed. 2005, 44, 4844;
(e) Assaf, K. I.; Nau, W. M. Cucurbiturils: From Synthesis to High-Affinity
Binding and Catalysis. Chem. Soc. Rev. 2015, 44, 394; (f) Ogoshi, T.; Yamag-
ishi, T. A.; Nakamoto, Y. Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes:
New Key Players for Supramolecular Chemistry. Chem. Rev. 2016, 116,
7937.
4. (a) Yamaguchi, N.; Gibson, H. W. Formation of Supramolecular Poly-
mers from Homoditopic Molecules Containing Secondary Ammonium Ions
and Crown Ether Moieties. Angew. Chem., Int. Ed. 2004, 38, 143; (b) Zhao,
Y.-L.; Dichtel, W. R.; Trabolsi, A.; Saha, S.; Aprahamian, I.; Stoddart, J. F. A
Redox-Switchable Α-Cyclodextrin-Based [2]Rotaxane. J. Am. Chem. Soc.
2008, 130, 11294; (c) Xue, M.; Yang, Y.; Chi, X.; Zhang, Z.; Huang, F. Pil-
lararenes, a New Class of Macrocycles for Supramolecular Chemistry. Acc.
Chem. Res. 2012, 45, 1294; (d) Nimse, S. B.; Kim, T. Biological Applications
of Functionalized Calixarenes. Chem. Soc. Rev. 2013, 42, 366; (e) Isaacs, L.
Stimuli Responsive Systems Constructed Using Cucurbit[n]uril-Type Mo-
lecular Containers. Acc. Chem. Res. 2014, 47, 2052; (f) Qi, Z.; Schalley, C. A.
Exploring Macrocycles in Functional Supramolecular Gels: From Stimuli
Responsiveness to Systems Chemistry. Acc. Chem. Res. 2014, 47, 2222; (g)
Strutt, N. L.; Zhang, H.; Schneebeli, S. T.; Stoddart, J. F. Functionalizing
Pillar[n]arenes Acc. Chem. Res. 2014, 47, 2631.
5. (a) Qu, D.-H.; Wang, Q.-C.; Zhang, Q.-W.; Ma, X.; Tian, H. Photore-
sponsive Host–Guest Functional Systems. Chem. Rev. 2015, 115, 7543; (b)
Murray, J.; Kim, K.; Ogoshi, T.; Yao, W.; Gibb, B. C. The Aqueous Supra-
molecular Chemistry of Cucurbit[n]urils, Pillar[n]arenes and Deep-Cavity
Cavitands. Chem. Soc. Rev. 2017, 46, 2479; (c) Wang, S. R.; Song, Y. Y.; Wei,
L.; Liu, C. X.; Fu, B. S.; Wang, J. Q.; Yang, X. R.; Liu, Y. N.; Liu, S. M.; Tian,
T.; Zhou, X. Cucurbit[7]uril-Driven Host-Guest Chemistry for Reversible
Intervention of 5-Formylcytosine-Targeted Biochemical Reactions. J. Am.
Chem. Soc. 2017, 139, 16903; (d) Datta, S.; Misra, S. K.; Saha, M. L.; Lahiri,
N.; Louie, J.; Pan, D. P. J.; Stang, P. J. Orthogonal Self-Assembly of an Or-
ganoplatinum(Ii) Metallacycle and Cucurbit[8]uril That Delivers Curcu-
min to Cancer Cells. Proc. Natl. Acad. Sci. U. S. A. 2018, 115, 8087; (e) Song,
N.; Kakuta, T.; Yamagishi, T.-a.; Yang, Y.-W.; Ogoshi, T. Molecular-Scale
Porous Materials Based on Pillar[n]arenes. Chem 2018, 4, 2029.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9. (a) Tan, L.-L.; Li, H.; Tao, Y.; Zhang, S. X.-A.; Wang, B.; Yang, Y.-W.
Pillar[5]arene-Based Supramolecular Organic Frameworks for Highly Se-
lective CO2-Capture at Ambient Conditions. Adv. Mater. 2014, 26, 7027; (b)
Tan, L.-L.; Zhu, Y.; Long, H.; Jin, Y.; Zhang, W.; Yang, Y.-W. Pillar[n]arene-
Based Supramolecular Organic Frameworks with High Hydrocarbon Stor-
age and Selectivity. Chem. Commun. 2017, 53, 6409.
10. (a) Ogoshi, T.; Sueto, R.; Yoshikoshi, K.; Sakata, Y.; Akine, S.; Yamag-
ishi, T.-a. Host–Guest Complexation of Perethylated Pillar[5]arene with Al-
kanes in the Crystal State. Angew. Chem., Int. Ed. 2015, 54, 9849; (b) Jie, K.
C.; Zhou, Y. J.; Li, E. R.; Li, Z. T.; Zhao, R.; Huang, F. H. Reversible Iodine
Capture by Nonporous Pillar[6]arene Crystals. J. Am. Chem. Soc. 2017, 139,
15320; (c) Jie, K.; Liu, M.; Zhou, Y.; Little, M. A.; Bonakala, S.; Chong, S. Y.;
Stephenson, A.; Chen, L.; Huang, F.; Cooper, A. I. Styrene Purification by
Guest-Induced Restructuring of Pillar[6]Arene. J. Am. Chem. Soc. 2017, 139,
2908; (d) Jie, K.; Zhou, Y.; Li, E.; Zhao, R.; Liu, M.; Huang, F. Linear Posi-
tional Isomer Sorting in Nonporous Adaptive Crystals of a Pillar[5]arene. J.
Am. Chem. Soc. 2018, 140, 3190; (e) Ogoshi, T.; Saito, K.; Sueto, R.; Kojima,
R.; Hamada, Y.; Akine, S.; Moeljadi, A. M. P.; Hirao, H.; Kakuta, T.; Yamag-
ishi, T. Separation of Linear and Branched Alkanes Using Host-Guest Com-
plexation of Cyclic and Branched Alkane Vapors by Crystal State Pil-
lar[6]arene. Angew. Chem., Int. Ed. 2018, 57, 1592; (f) Jie, K.; Zhou, Y.; Li,
E.; Huang, F. Nonporous Adaptive Crystals of Pillararenes. Acc. Chem. Res.
2018, 51, 2064; (g) Li, E.; Zhou, Y.; Zhao, R.; Jie, K.; Huang, F. Dihaloben-
zene Shape Sorting by Nonporous Adaptive Crystals of Perbromoethylated
Pillararenes. Angew. Chem., Int. Ed. 2019, 58, 3981.
6. (a) Lee, S.; Chen, C. H.; Flood, A. H. A Pentagonal Cyanostar Macro-
cycle with Cyanostilbene CH Donors Binds Anions and Forms Dial-
kylphosphate [3]Rotaxanes. Nat. Chem. 2013, 5, 704; (b) Barnes, J. C.; Ju-
ricek, M.; Strutt, N. L.; Frasconi, M.; Sampath, S.; Giesener, M. A.; McGrier,
11. Hu, X. B.; Chen, Z. X.; Chen, L.; Zhang, L.; Hou, J. L.; Li, Z. T. Pil-
lar[n]arenes (n=8-10) with Two Cavities: Synthesis, Structures and Com-
plexing Properties. Chem. Commun. 2012, 48, 10999.
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Journal of the American Chemical Society
Page 8 of 9
12. (a) Garcia Villaluenga, J. P.; Tabe-Mohammadi, A. A Review on the
Polycrystalline Electrode. Collect. Czech. Chem. Commun. 2009, 74, 611; (b)
Choe, S.; Lee, S. H.; Chang, Y. Y.; Hwang, K. Y.; Khim, J. Rapid Reductive
Destruction of Hazardous Organic Compounds by Nanoscale Fe-0. Chemo-
sphere 2001, 42, 367.
Separation of Benzene/Cyclohexane Mixtures by Pervaporation Processes.
J. Membr. Sci. 2000, 169, 159; (b) Jie, K. C.; Zhou, Y. J.; Li, E. R.; Zhao, R.;
Huang, F. H. Separation of Aromatics/Cyclic Aliphatics by Nonporous
Adaptive Pillararene Crystals. Angew. Chem., Int. Ed. 2018, 57, 12845.
13. Liu, M. H.; Han, M. F.; Yu, W. W. Hydrogenation of Chlorobenzene
to Cyclohexane over Colloidal Pt Nanocatalysts under Ambient Conditions.
Environ. Sci. Technol. 2009, 43, 2519.
14. Butler, E. C.; Hayes, K. F. Kinetics of the Transformation of Trichlo-
roethylene and Tetrachloroethylene by Iron Sulfide. Environ. Sci. Technol.
1999, 33, 2021.
1
2
3
4
5
6
7
8
17. (a) IARC. IARC Monogr. Eval. Carcinog. Risks Hum. 1999, 71, 589−
602; (b) U.S. Environmental Protection Agency. 1,4-Dioxane (1,4-Diethy-
leneoxide). https://www.epa.gov/sites/production/files/2016-09/docu-
ments/1-4-dioxane.pdf (accessed Sept 9, 2016); (c) Guidelines for Drinking-
Water Quality, 4th ed.; World Health Organization: Geneva: 2011; pp 363-
364.
18. Huang, G.; Jiang, Y.; Yang, S.; Li, B. S.; Tang, B. Z. Multistimuli Re-
sponse and Polymorphism of a Novel Tetraphenylethylene Derivative. Adv.
Funct. Mater. 2019, 29, 1900516.
9
15. Meharg, A. A.; Wright, J.; Osborn, D. Chlorobenzenes in Rivers
Draining Industrial Catchments. Sci. Total Environ. 2000, 251, 243.
16. (a) Musilova-Kebrlova, N.; Janderka, P.; Trnkova, L. Electrochemical
Processes of Adsorbed Chlorobenzene and Fluorobenzene on a Platinum
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
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26
27
28
29
30
31
32
33
34
35
36
37
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39
40
41
42
43
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45
46
47
48
49
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