A Self-Assembled Trigonal Prismatic Molecular Vessel for Catalytic Dehydration Reactions in Water

Article abstract of DOI:10.1002/chem.201702263

A water-soluble Pd₆ trigonal prism (A) was synthesized by two-component coordination-driven self-assembly of a Pd^II 90° acceptor with a tetraimidazole donor. The walls of the prism are constructed by three conjugated aromatic buildin

Full text of DOI:10.1002/chem.201702263

A Journal of
Accepted Article
Title: A Self-Assembled Trigonal Prismatic Molecular Vessel for
Catalytic Dehydration Reactions in Water
Authors: Partha Sarathi Mukherjee, Paramita Das, Atul Kumar, and
Prodip Howlader
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A Self-Assembled Trigonal Prismatic Molecular Vessel for
Catalytic Dehydration Reactions in Water
Paramita Das,a# Atul Kumar,a# Prodip Howlader,a and Partha Sarathi Mukherjeea,*
Dedication ((optional))
Abstract: A water-soluble Pd6 trigonal prism (A) was synthesized by
two-component coordination-driven self-assembly of a Pd(II) 90°
acceptor with a tetraimidazole donor. As the walls of the prism are
constructed by three conjugated aromatic building blocks, the
confined pocket of the prism is hydrophobic. In addition to the
hydrophobic cavity, large product egress windows make A an ideal
molecular vessel to catalyze otherwise challenging pseudo
multicomponent dehydration reactions in its confined nanospace in
aqueous medium. This study is an attempt towards selective
generation of the intermediate tetraketones and xanthenes by fine-
tuning the reaction conditions employing a supramolecular molecular
vessel. Moreover, poor or no yield of the dehydrated products in
absence of A under similar reaction conditions ascertains the
ubiquity of the confined space of the barrel in promoting such
reactions in water. Furthermore, we focussed on the rigidification of
the tetraphenylethylene-based tetraimidazole unit anchored within
the Pd(II) coordination architecture; enabling counter-anion
dependent aggregation induced emission in presence of water.
to engineer polyimidazole-functionalized supramolecules without
template. In this quest, several groups have contributed
template-free supramolecular assemblies paving access to rare
structures.8 The nanoscopic confined space that is endowed with
desired functionality provides the impetus for applications in
selective
encapsulation,9 molecular flasks,10 gas adsorption, sensing,
separation, bioengineering and so on.11
Among the many potential applications of container molecules,
the one which has made very attractive in the last several years
is their ability to catalyze reactions of bound guests12 in aqueous
media13 reminiscent of enzyme catalysis. Although many striking
results have been reported in the field of supramolecular
catalysis, the biggest challenge in establishing a catalytic cycle
is product inhibition.14 Albeit a few enticing examples are
reported for cavity-induced organic transformations, but their
statistics are limited in the Diels-Alder,15 epoxidation,16 the aza-
Cope rearrangement,17 Knoevenagel reaction,18 Nazarov
cyclization,19 sigmatropic rearrangements, and a few others.20
Again reversible dehydration condensation in aqueous media is
a difficult transformation and remains an important challenge
because the large excess of water drives the equilibrium
backward.21 While most of the examples accomplished inside
molecular cavities are thermal12e and photochemical organic
Introduction
In the past two decades perceptible progress has been made in
the self-assembly of elaborately designed diverse tectons
encrypted with explicit information in specific stoichiometric
ratios. Thus, preprogrammed thermodynamically favorable
abiological supramolecular architectures with well-defined
shapes and sizes can be afforded using appropriate building
blocks.1 This enables the construction of a suite of finite
supramolecular coordination complexes (SCCs), from two-
dimensional (2-D) polygons to three-dimensional (3-D) cages,
prisms, bowls, tubes and capsules.2,3 Unified under the principle
of open window and easy ingress and egress of guests, distinct
barrel-shaped structures by metal−ligand self-assembly remain
very challenging and limited examples are reported in the
literature.4 Again non-covalent cages are of particular interest
because of circumvention of tedious multistep synthesis which is
obligatory for covalent analogs.5 Furthermore, the intriguing
features of an imidazole donor over a pyridyl donor6 and the
declining fame of templates7 have appealed synthetic chemists
transformations,13b e dehydration condensation reactions in
-
supramolecular microenvironment are infrequent. On the
contrary, enzymes can readily achieve the dehydration in water
even under neutral conditions at ambient temperature which
hard pressed the synthetic chemists to construct such well-
furnished catalytic frameworks.
On the other hand, various applications of fluorescent
chromophores22 24 have captured much attention of the
-
contemporary researchers motivating them to develop novel
fluorophores with the aspiration to explore new smart molecular
devices.25 Conventional fluorophores recurrently display highly
emissive fluorescence in dilute solutions but suffer severely from
aggregation-caused quenching (ACQ) in concentrated solutions
or in the condensed state owing to the formation of excimers
and exciplexes that restrain their practical applications.26 In
contrast,
a contrary effect known as aggregation-induced
emission (AIE), wherein fluorogens that endure non-radiative
decay through intramolecular rotations/vibrations at low
concentrations emit intense fluorescence in the condensed
state.27 Thus, the discovery and development of AIE luminogen
molecules have attracted pervasive attention.28 Again, non-
covalent self-assembled AIEgens engross special attention over
[a]
P. Das, A. Kumar, P. Howlader, Prof. P. S. Mukherjee
Inorganic and Physical Chemistry Department
Indian Institute of Science
Bangalore-560012, India
E-mail: psm@ipc.iisc.ernet.in
FAX: 91-80-23601552
covalent AIEgens.29 In the present context, it is pertinent to
27
mention that the “AIE phenomenon”
has enthralled the
contemporary chemists to design such AIE-active fluorophores.
Furthermore, the concept of “light-emitting tetraphenylethylene
(TPE)-based architectures on SCC platforms” by Stang et al.30
#These authors have equal contributions
Supporting information for this article is given via a link at the end of
the document (CCDC:1550021, 1550022, 1550023, 1550024,
1550025).
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has exemplified their multifaceted applications in sensor devices, With TPE-based donor (L) in hand, two-component A was
advanced optoelectronic materials and so on. Although quite a
few light-emitting TPE-based discrete organoplatinum(II)
metallacycles and metallacages are reported,29 AIE active
obtained by adding an aqueous solution of cis-(tmen)Pd(NO3)2
(M) into the solid tetratopic donor L in 2:1 molar ratio followed by
subsequent stirring at 50 °C for 6 h. The resulting clear solution
was triturated with acetone to obtain self-assembled [6+3]
molecular barrel A [M6L3] as an off-white precipitate in pure form.
aqueous TPE-Pd-metallacage is yet to be explored. Again, Pd2
+
is an ‘open-shell’ transition-metal ion and is notorious for its
fluorescence quenching effect.31 Considering this effect of Pd2+ in
diminishing fluorosence quantum efficiency, synthesis of Pd(II)
containing fluorescent metallacage is quite challenging.
1
A was highly soluble in water. It was characterized by H NMR
spectroscopy (Figure 1b), DOSY (Figure S3, Supporting
Information), COSY (Figure S4, Supporting Information) and ESI-
MS (Figure S5, Supporting Information). 1H NMR analysis of A in
D2O exhibited sharp distinct peaks with noticeable downfield
shift as compared to the ligand L which is expected owing to the
coordination of L to Pd(II). The peaks of A were assigned with
the help of the 1H−1H COSY spectra.
Herein, we report a template-free synthesis of a water-soluble
trifacial molecular barrel A via two-component self-assembly of
TPE–functionalized tetraimidazole donor L with 90° acceptor cis-
Pd(tmeda)(NO3)2 (M) [tmeda = N,N,N',N'-tetramethylethane-1,2-
diamine, L = 1,1,2,2-tetrakis(4-(1H-imidazol-1-yl)phenyl)ethene]
(Scheme 1). This newly engineered water-soluble molecular
barrel with integrated hydrophobic pocket has shown to be
suitable for otherwise difficult dehydration reactions of water-
insoluble guests in aqueous medium to form xanthene
derivatives. To the best of our knowledge, the nanobarrel A
represents the first example of a discrete self-assembled
molecular vessel as a catalyst for the selective generation of
both tetraketone intermediates and xanthenes in
a
homogeneous aqueous environment under mild reaction
conditions. It is worth affirming that in absence of the cage, same
reactions preceded sluggishly giving either poor or no yields of
the non-cyclized tetraketones or cyclized xanthenes. This defines
the significance of the confined cavity in promoting such
unfavorable reactions in aqueous media. Additionally, for the first
time, we have explored the AIE behavior of this Pd(II) containing
metallacage in aqueous medium. Rigidification of the TPE-based
linker (L) to Pd(II) acceptors within a SCC matrix confers the
counter-anion dependent AIE properties in our synthesized
molecular barrel A.
Figure 1. Partial 1H NMR spectra of (a) ligand L recorded in CDCl3, and (b)
complex A recorded in D2O.
Notably, diffusion-ordered NMR spectroscopy (DOSY, D2O)
corroborated the formation of
a single species by the
10
appearance of a clear single band at D = 1.5488×10- m2/s (log
D = −9.81) with a hydrodynamic radius of about 12.81 Å
(Supporting Information). ESI-MS spectra of the A (after anion
¯
exchange with PF6 ) in acetonitrile displayed three salient peaks
Scheme 1. Schematic representation of the formation of 3D molecular barrel
A.
at m/z = 1476.66, 1071.26 and 828.21 with isotopic distribution
3
4
+
patterns corresponding to [A(PF6)9] , A(PF6)8] and [A(PF6)7]5
+
+
charge fragments respectively (Figure S5), attesting the
formation of a M6L3 species. Finally, diffraction quality single
crystals were obtained by slow vapor diffusion of acetone into an
aqueous solution of complex A at room temperature for two
weeks.
Results and Discussion
Synthesis and Characterization
Single crystal XRD analysis of complex A unequivocally
confirmed the formation of a trifacial barrel containing open
windows (Figure 2, CCDC 1550021). The vertices of the barrel
were occupied by Pd(II) ions. Structural refinements revealed that
the distance between the metal ions (Pd···Pd distance) within
one equilateral triangle is about 15 Å. Two of these triangles
L was synthesized in two steps, starting from TPE precursor
following the reported procedure.32 It was fully characterized by
IR, melting point, 1H (Figure 1a), 13C NMR, ESI-MS spectrometry,
and its molecular structure was determined by single-crystal X-
ray diffraction (XRD) analysis (CCDC 1550022) (Supporting
Information).
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were linked by the ligand L to construct the barrel which makes
the closest distance between the metal ions (two triangles) ca. 12
Å having an approximate volume of 1169 Å3. Molecular
orientation in the crystal lattice shows the formation of a channel
type of structure along the c-axis with slight interpenetration
between alternative channels of barrels (Figure S6, Supporting
Information). Important crystallographic data and refinement
semi-empirical method with a PM6 basis set (Figure S15,
Supporting Information). As the aldehyde group is more polar
than the aromatic ring of naphthaldehyde, it may lean outside
the cavity. However, the naphthyl moieties are stabilized inside
the hydrophobic cavity of the cage by CH–π stacking
interactions with the phenyl rings of the walls (L) of the cavity
further throwing light (specifying the reason) for the splitting of
the phenyl peak in 1H NMR spectra (Figure S7b). Encapsulations
of the bulkier substrates were monitored by absorption
spectroscopy (Figure S16-21, Supporting Information). Thus, we
hypothesized that A would be adept to act as a molecular
nanovessel to catalyze classic organic reactions in green
aqueous medium.
parameters of
A are provided in Table S2 (Supporting
Information).
Catalytic Activity and Regulation
Xanthenes, a special branch of pyran systems are important
building blocks of many natural products and possess potential
applications in medicinal chemistry as well as fluorescent
materials.33 Again tetraketones and their tautomeric enol forms
are the basic intermediates for the preparation of biologically
relevant heterocyclic compounds and numerous acridinones as
laser dyes.34 Capitalizing the enormous applications and
recognition of the aforementioned compounds and in
continuation of our quest for performing dehydration reactions in
aqueous media,5c,6d we employed water-soluble A as an efficient
and homogeneous catalyst for the one-pot pseudo three-
component synthesis of tetraketones (3) and their corresponding
xanthenes (4) in water. Furthermore, the tetraketones (3) are
prone to cyclization by the elimination of water affording the
corresponding xanthenes (4). In some instances, the driving
force of dehydration is so enhanced that the intermediate 3
cannot be isolated and the reaction affords only 4. Conversely,
the number of domino reactions for the synthesis of intermediate
3 is scarcer compared to 4. To evade this problem, we wish to
disclose the first development and implementation of a 3D
Figure 2. Single crystal XRD structure of the cage A (a) side view; and (b) top
view. Color codes: yellow-Pd, blue-N, dark grey-C (CCDC 1550021). Hydrogen
atoms are omitted for clarity.
Encapsulation Studies
The interior cavity of A has hydrophobic pocket fenced by the
three aromatic walls (L). This enthused us to study the prospect
of encapsulating water-insoluble aromatic guest in an aqueous
medium. Our investigations started with 2-naphthaldehyde (1i) as
a test sample. An excess amount of 1i was suspended in an
aqueous solution of A at room temperature. As anticipated, 1i
was encapsulated in A which was confirmed by the substantial
up-field shifts of the 1H NMR signals of the encapsulated guests.
1
Notably, 1i was not sufficiently water soluble to permit their H
NMR spectra to be recorded in D2O in the absence of hosts.
Moreover, encapsulations caused splitting of the H4 and H5
protons on the phenyl rings of the ligand (L) (hitherto at 7.27 ppm
in A) into two doublets of equal intensity (Figure S7, Supporting
Information). This is attributed to the strong CH–π interaction of
the guest molecules with the walls of the cavity. The
stoichiometry of cage vs. guest was evaluated to be 1 : 3 from
nanocage as
a homogeneous catalyst for the selective
generation of both cyclized xanthenes (4) and non-cyclized
tetraketone intermediates (3) under two different conditions.
To optimize the reaction conditions, a series of experiments was
conducted with an illustrative reaction of 2-naphthaldehyde (1i)
(0.02 mmol) and dimedone (2a) (0.04 mmol) with a variation of
reaction parameters, such as catalyst, reaction temperature etc.,
and the results are summarized in Table 1. The results
established that the temperature of the reaction had a significant
effect on the yield of the non-cyclized product (3i) to cyclized
product (4i). The initial reaction was performed in the presence of
5 mol% A in H2O at room temperature (r.t.). After extraction of the
reaction mixture with CDCl3, the 1H NMR diagnosed the
formation of the non-cyclized product (3i). Albeit, 1 mol% catalyst
afforded the desired product (3i) in poor yield. With 10 mol% of
catalyst, no significant improvement in the yield was observed. In
contrast, on repeating the same experiment at 60 °C with 5 mol%
catalyst yielded only the cyclized product (4i) in 90% yield. This
could probably be due to the ease of elimination of H2O at a
higher temperature in the hydrophobic cavity of the cage.
Reducing the catalyst to 1 mol% afforded 4i in only 19% yield with
1
the H NMR spectra (Figure S8, Supporting Information). Again
DOSY NMR exhibited identical diffusion coefficients for the
guest (1i) and the host cage (Figure S9, Supporting Information).
The peaks of the inclusion complex 1i⊂A (⊂ denotes
1
encapsulation) were assigned with the help of the H–1H COSY
spectra (Figure S10, Supporting Information). Recognition of
1i⊂A was further scrutinized by UV-Vis spectroscopy where
additional bands along with cage peaks assigned to the guest
molecule were witnessed (Figures S11 and S12, Supporting
Information). Additionally 1:3 stoichiometry is obtained based on
1
UV-Vis studies (Supporting Information). The peak at 1686 cm−
in infrared spectroscopy was attributed to the stretching of
aromatic CH=O bond, suggesting the encapsulation of 1i by the
host (Figure S14, Supporting Information). The host-guest (1 : 3)
complex was modeled and the structure was optimized using
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<5% of 3i at 60 °C. It was found that at 50 °C, 5 mol% catalyst
could afford mainly non-cyclized 3i (76%) along with the very
small amount of cyclized 4i (15%) after 24 h. In hope of higher
yields, further optimizations were performed
hydrophobic nature of the cage can assist elimination of H2O at
a sufficiently low temperature in an aqueous medium. This
stands in stark juxtaposition to xanthene synthesis in bulk
solution, which generally requires heating to reflux in neat or in
an organic solvent.
Further, the scope of A as a catalyst was examined using a suite
of aldehydes to synthesize the non-cyclized products (3) as well
as cyclized products (4) under two different conditions and the
results are presented in Tables 2 and 3, respectively. Despite the
difficulty of a Knoevenagel condensation reaction with electron-
rich carbonyl, the reaction occurred successfully with 4-methyl
benzaldehyde, 3-methoxy benzaldehyde. The versatility of the
reaction was established since aldehydes with neutral and
electron-withdrawing groups at o-, m- and p-positions all afforded
moderate to good yields in the presence of A. It was pleasing to
find that sensitive aldehydes (containing a heteroatom, and CF3
groups) also reacted very efficiently with no side reactions.
Despite the mild conditions, even sterically bulky 1-naphthyl and
2-naphthyl aldehydes were easily transformed into the desired
products in good yields. However, the relative reaction rate was
decreased with bulkier 1-pyrenealdehyde as evident from the
reaction completion time (48 h). This size-selective catalysis
provides evidence about the involvement of cavity of A. The
scope of the reaction was further expanded using 1,3-
cyclohexadione.
Table 1. Optimization of Reaction Conditions for the Dehydration reactionsa
Entry
Catalyst
(mol%)
Temp
(°C)
Time
(in h)
% Yields
Tetraketon
e (3i)b
% Yields
Xanthene
(4i)b
1
2
A (05)
A (01)
A (10)
A (05)
A (01)
A (10)
A (05)
A (05)
L (15)
L (15)
M (30)
M (30)
-
r.t.
r.t.
r.t.
60
60
60
50
80
r.t.
60
r.t.
60
r.t.
60
12
12
12
12
12
12
48
12
24
24
24
24
24
24
90
-
22
3
91
4
-
90
Table 2. Nanobarrel “A” Catalyzed r.t. Synthesis of Non-cyclized Producta
5
<5
19
6
-
90
7
76
15
8
-
-
-
-
-
-
-
91
9
-
-
-
-
-
-
Product (% Yields)b
10
11
12
13
14
Entry
Ar (1)
R
Prod
uct
(3)
Time
(in h)
without A
with A
99
1
2
Ph
Me (2a)
Me (2a)
Me (2a)
Me (2a)
Me (2a)
Me (2a)
Me (2a)
Me (2a)
Me (2a)
Me (2a)
Me (2a)
3a
3b
3c
3d
3e
3f
02
02
02
02
02
02
02
02
12
12
48
30
22
25
35
30
30
27
30
-
-
4-Me-Ph
3-OMe-Ph
4-Br-Ph
96
a: Aldehydes 1 (0.02 mmol), cyclic 1,3-diketones 2 (0.04 mmol), 1 mL water,
stirring. b: Crude yields determined from 1H NMR based on starting materials.
3
98
4
99
at 80 °C, but no improved results were obtained. Importantly, no
product was observed (cyclized as well as non-cyclized) without
any catalyst which further necessitates the importance of
hydrophobic cavity in this transformation. Moreover, reactions
did not proceed when control experiments with individual cage
components like ligand L (15 mol%), and cis-(tmen)Pd(NO3)2 (M)
(30 mol%) were performed at r.t. and 60 °C.
Temperature dependence on the yield of non-cyclized product
(3i) to the cyclized product (4i) was probed with the same test
reaction with 5 mol% of catalyst A in H2O (1 mL) for 12 h at
various temperatures with an increment of 10 °C (Figure S22,
Supporting Information). Reaction results established that
5
2,4-(Cl)2-Ph
3-Br-Ph
99
6
98
7
4-CF3-Ph
Py-4-al
3g
3h
3i
98
8
99
9
2-naphthyl
1-naphthyl
1-pyrene
90
10
11
3j
-
91
3k
-
92
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systems (Table 3). This reaction efficiently resulted in the
formation of six chemical bonds (4 C–C, 2 C–O) and two 4H-
pyran units in a single operation.
12
13
14
4-Cl-Ph
H (2b)
H (2b)
3l
3m
3n
02
12
48
35
97
88
82
2-naphthyl
-
-
All the compounds were obtained with high purity by simple
filtration as evident for 1H NMR spectra and column
chromatography was not obligatory. The structures of
compounds 3k (CCDC 1550025) and 4j (CCDC 1550023) were
clearly determined using X-ray crystallography (Figures S23-24,
Supporting Information). The most striking observation arose
when 9-anthraldehyde was employed. No progress was
witnessed beyond Knoevenagel condensation even after 7 days,
probably because of steric reasons (Figure S25, CCDC 1550024,
Supporting Information). Furthermore, under similar reaction
conditions, in absence of the cage the dehydration reactions
afforded poor or no yield of the non-cyclized tetraketones or
cyclized xanthenes. This essentially reflects the role of
hydrophobic confined space of the barrel in endorsing such
unfavorable dehydration reactions in water. It is pertinent to
mention that in case of the intermediate tetraketone synthesis,
the poor background reaction in absence of catalyst for smaller
mono benzene substituted aldehydes can be attributed to their
partial solubility in water.
Terephthala
ldehyde
Me (2a)
a: Aldehydes 1 (0.02 mmol), cyclic 1,3-diketones 2 (0.04 mmol), catalyst A (5
mol%), water (1 mL), r.t. stirring. b: Crude yields determined from 1H NMR based
on starting materials.
Table 3. Barrel “A” Catalyzed Snthesis of Xanthenes at High Temperaturea
Entry
Ar (1)
R
Produ
ct
Time
(in h)
Product (%
Yields)b
(4)
without
with
A
A
The recyclability of A was also examined in the model reaction
of 1i and 2a. After extraction of the reaction mixture with CDCl3,
the addition of further aliquots of 1i and 2a showed that the
substrate continues to react just as fast as the first cycle of the
experiment, for at least four times without much loss of catalytic
activity (Figure S26, Supporting Information). The recycled
catalyst was characterized by IR, ESI-MS spectroscopy (Figure
S27-28, Supporting Information). After abstraction of the product
in CDCl3, the NMR spectra showed no trace of L, which
indicated that the A was not collapsed or decomposed during
the reaction.
1
2
3
4
Ph
Me(2a)
Me(2a)
Me(2a)
Me (2a)
4a
4b
4c
4d
02
02
02
02
-
99
99
96
98
4-Me-Ph
3-OMe-Ph
4-Br-Ph
-
-
-
5
6
2,4-(Cl)2-Ph
3-Br-Ph
Me(2a)
Me(2a)
Me(2a)
Me(2a)
Me(2a)
Me(2a)
Me(2a)
H (2b)
H (2b)
H (2b)
H (2b)
4e
4f
02
02
02
02
12
12
48
02
12
12
48
-
-
-
-
-
-
-
-
-
-
-
97
99
98
99
90
91
88
97
89
87
86
A plausible reaction cascade for the catalytic cycle is shown in
Figure 3. The reaction commences with the encapsulation of the
aromatic aldehyde 1 within the hydrophobic cavity of the cage
(Step I). 5,5-dimethylcyclohexane-1,3-dione 2a, which is water
soluble exists in equilibrium with its enolate form (a) due to its
low pKa (4.34).35 Compound a reacts with the encapsulated
aldehyde to generate oxyanion intermediate followed by rapid
loss of water to generate Knoevenagel product b [Step II]. Again,
the reaction of a subsequent molecule of a with b generates
another oxyanion intermediate. This intermediate takes a proton
from water to afford the non-cyclized product 3 [Step III]. The
product 3 being too large to be fully encapsulated in the cavity
came out of the cage [Step IV] and finally precipitated during the
course of the reaction at room temperature. However, when the
reaction is performed at higher temperature (60 °C), the
intermediate 3 acquires sufficient activation energy to allow the
prompt exclusion of water before parting the cage. This
dehydration is further aided by the hydrophobic cavity of A to
generate the dehydrated product 4 [Step V]. Owing to the bulky
nature of the product, it spontaneously comes out of the cage
that results in the completion of the catalytic transformation [Step
VI]. We hypothesized that the anionic intermediates are
7
4-CF3-Ph
Py-4-al
4g
4h
4i
8
9
2-naphthyl
1-naphthyl
1-pyrene
4-Cl-Ph
10
11
12
13
14
15
4j
4k
4l
2-naphthyl
1-naphthyl
1-pyrene
4m
4n
4o
16
Terephthalal
dehyde
Me (2a)
4p
48
-
85
a: Aldehydes 1 (0.02 mmol), cyclic 1,3-diketones 2 (0.04 mmol), catalyst A (5
mol%), water (1 mL), stirring and heating at 60 °C. b: Crude yields determined
from 1H NMR based on starting materials.
The efficiency of these processes was extra stretched to exhibit
the double multicomponent processes by utilizing bis-1,4-
aldehyde in an analogous manner to furnish the respective bis-
stabilized by the Pd2 centers located at every portal of the cage.
+
In order to garner further mechanistic insights as well as to
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determine that dehydration in Step V is facilitated inside the
hydrophobic cavity, further control experiments were conducted.
When the empty cage A was externally treated with diol 3i, no
trace of 4i was formed even after 48 h of stirring at 60 °C. Also
when B was externally treated with diol 3i and stirred at room
temperature for 48 h no encapsulated diol was found inside B in
1H NMR. But when in situ reaction was performed with aldehyde
1i, 2a and A at r.t., the presence of traces of diol 3 in the
resulting aqueous solution indicates its encapsulation inside the
cage (Figure S29-S31, Supporting Information). These attested
that (i) at r.t. once 3 is formed, it steps out of the cage and
becomes benchtop stable; no hydrophobic abetted dehydration
takes place, (ii) when
Figure 3. Probable catalytic cycle for the dehydration reactions in the presence of A.
reaction is carried out at 60 °C, dehydration occurs prior to
exclusion of in-situ synthesized diol leading to cyclized product
and (iii) that the reaction pathway leading to 4 is possible inside
the cavity of A.
inherent error-correction,1d and defect-free assembly,1e facile and
fast formation,2f increased solubility. These facilitate solution-
based characterizations owing to their discrete nature.2h,44
Our investigations into this field inaugurated with the correct
selection of solvent mixtures (good solvent/poor solvent), as the
duo solvent played an imperative role in observing the AIE
effect. Lots of efforts were therefore made in the early stage,
probing for an appropriate solvent system, and finally,
acetonitrile (ACN)/water was selected as the best solvent system
for such supramolecular aggregation. To this end, we prepared
the hexafluorophosphate analogue of the barrel after anion
exchange with PF6¯salt [A(PF6¯)] which was soluble in
acetonitrile. This assembly was characterized by 1H NMR
spectroscopy (Figure S32, Supporting Information), DOSY
(Figure S33, Supporting Information) and ESI-MS (Figure S5,
Supporting Information).
Photophysical Studies of Trigonal Barrel A
Tetraphenylethylene (TPE) is an iconic AIE fluorophore in which,
restricted phenyl-ring rotation and ethylenic C=C bond twist on
aggregation in the condensed state induce its fluorescence.36
Recent studies revealed that the aggregation of TPE
chromophores is not the only way to “turn on” the emission;
these conformational changes can be accomplished by other
strategies such as covalent modifications,37 host−guest
chemistry,38 coordination,39 hydrogen bonding,40 π−π stacking,41
electrostatic interactions42 and embedding into metal−organic
frameworks.43 Although many interesting results have been
reported in the field of TPE-based MOFs, in our view the area of
light-emitting metal−organic materials based on SCC platforms is
still in a premature stage. SCCs preserve the attractive features
of MOFs, yet also afford circumvention of synthetic steps,1a
The absorption spectra of L and cage [A(PF6¯)] in acetonitrile are
shown in Figures S34 and S35 (Supporting Information). L
displayed broad absorption bands centered at 267 and 320 nm
1
1
with a molar absorption coefficient (ε) of 2.16 × 104 M− cm− and
1
1
1.03 × 104 M− cm− , respectively. Upon the formation of
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10.1002/chem.201702263
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35
30
25
20
15
10
5
metallacage [A(PF6¯)], the lowest energy band marginally red-
shifted (ca. 5 nm). [A(PF6¯)] exhibits two absorption bands
centered at 290 and 325 nm with (ε) = 3.82 × 104 and 2.72 × 104
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
1
1
M− cm− , respectively.
Ligand L is weakly emissive at ca. 395 nm in ACN (Figure 4)
because of non-radiative decay. However, immobilizing the
weakly emissive TPE ligand within a SCC platform causes
partial rigidification and stemming of the motions of the phenyl
rings in [A(PF6¯)] inducing some fluorescence enhancements.
The emission maximum of [A(PF6¯)] underwent a moderate red
shift from 395 to 470 nm in ACN at room temperature which is
manifested due to the melding effect of rigidification from
metallacage formation and new metal-to-ligand charge-transfer
(MLCT) processes upon coordination.29b However, the limited
fluorescence enhancement suggests that the TPE units are not
sufficiently rigidified to remove non-radiative decay pathways
and also the presence of palladium centers may cause an
emission quenching, due to their heavy atom effects. Notably,
[A(PF6¯)] showed 5.12-fold fluorescence enhancement over L. To
examine whether [A(PF6¯)] is still AIE alive, the emission spectra
in ACN/H2O solutions was recorded. The emission intensity
remained low in mixed solutions with water content less than
80%. However, upon further increment to 90%, the fluorescence
intensity abruptly increased (Figure 5). At 95% water fraction, the
emission intensity was approximately 5.45-fold higher than that
of its molecularly dispersed species in ACN (Figure S37,
Supporting Information). Meanwhile, its emission maximum
underwent a ca. 25 nm red shift which is ascribed to the charge-
transfer (CT) process within the assemblies in a polar solution.45
0
350
400
450
500
550
600
Wavelength (nm)
Figure 5. Fluorescence emission spectra of [A(PF6¯)] versus water fraction in
ACN/H2O mixtures (λex = 325 nm, c = 10.00 μM).
The AIE characteristics of [A(PF6¯)] in mixed solutions were
further probed by changes in quantum yields (ΦF) using quinine
sulfate as a reference. In ACN, relatively low ΦF values were
determined for L (0.02%) which increased to 0.2% for [A(PF6¯)] in
ACN and further enhanced to 1.56% at 95% water fraction.
The solid-state normalized absorption and emission spectra of L
and [A(PF6¯)] are shown in Figures S38 and S39, respectively. L
displayed broad absorption bands centered at 280 and 335 nm.
The fluorescence peak observed for solid L is likely to be red-
shifted (ca. 5 nm) which is attributed to the formation of excimeric
species.43c Likewise, [A(PF6¯)] exhibited a broad absorption band
centered at 400 nm which is moderately red-shifted ca. 75 nm
compared to the lowest energy band. However, [A(PF6¯)]
fluoresces in the solid state with a band centered at 507 nm (ca.
37 nm red-shifted with respect to dilute solution). The solid-state
quantum yield of [A(PF6¯)] was measured to be 2.72% which was
higher than that determined for the 95% water fractions (1.56%),
consistent with an AIE mechanism. In spite of the low quantum
yield value, keeping in mind the strong fluorescence quenching
effect of Pd2+ ion, it is worth mentioning.
The solvent effects on the emission profiles were also examined.
Because of the CT processes within the assemblies, increasing
the polarity of the solvent resulted in a quite regular red shift in
the emission maximum.45 The absorption and emission profiles
for [A(PF6¯)] in diverse solvents can be found in Supporting
Information (Figures S40 and S41). Again, the homogenous
nature of the ‘solutions’ proposed that the aggregates are of
nano-dimensions. Consequently, TEM investigation was
conducted to provide further insight into the size, shape and
morphology of the obtained aggregates. In mixtures with low
water content (30%), [A(PF6¯)] self-assembles into irregular
nanoparticles. When the water content becomes moderate (50%),
it forms regular nanospheres. Such regular nanospheres were
further gathered to form bead-like structures at 70% and
converted into cross-linking bead microstructures at higher water
contents (90%, Figures S42a−d). DLS experiments were
performed further to investigate the aggregation process. As
shown in Figure S43, when the water content increased from 30
to 70%, the average hydrodynamic diameters (Dh) exhibited a
gradual increase from 118 to 1126 nm, which indicated a
600
500
L
[A(PF6¯)]
400
300
200
100
0
350
400
450
500
550
600
Wavelength (nm)
Figure 4. Fluorescence emission spectra of L (λex = 320 nm, c = 10.00 μM) and
[A(PF6¯)] in ACN (λex = 325 nm, c = 10.00 μM).
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10.1002/chem.201702263
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gradual aggregation process. At higher water contents, visible
particles became dispersed in the ACN/H2O mixture, which
renders the system unsuitable for DLS measurements.
Synthesis of A.
cis-(tmen)Pd(NO3)2 (M) (34.8 mg, 0.10 mmol) was dissolved in 3 mL H2O
and the yellow clear solution was added to the solid ligand L (30.0 mg,
0.050 mmol) and was heated at 50 °C with stirring for 6 h. The solution
turned colorless with the consumption of the donor. After the completion
of the reaction, the mixture was filtered, concentrated under reduced
pressure, and the pure form of complex A was obtained as off-white
CONCLUSIONS
This article reports the synthesis of a water-soluble PdII trigonal
1
powder by trituration with acetone (Isolated yield: 55.1 mg, 85%). H NMR
6
(400 MHz, D2O): δ = 8.64 (12H, s, H1), 7.52 (24H, d, J=17.2 Hz, H2 and H3),
7.27 (48H, s, H4 and H5), 3.09 (24H, s, CH2), 2.74 (72H, s, CH3). IR ῦ: 3414,
3242, 3115, 2908, 2358, 1632, 1523, 1470, 1327, 1272, 1127, 1067,
prism via coordination-driven self-assembly without using any
template. The barrel was fully characterized by X-ray and other
spectroscopic techniques. The confined nanospace of the barrel
was successfully used as a molecular vessel for the synthesis of
a series of xanthenes via dehydration reaction in aqueous
medium under mild reaction condition without using any external
catalysts/additives. Such kind of xanthene synthesis generally
proceeds via tetraketone intermediates followed by in-situ
dehydration at high temperature in anhydrous medium. Our
present approach provides a pavement for selective isolation of
both cyclized xanthenes and their corresponding non-cyclized
intermediates just by mere changing of reaction temperature.
While dehydration reactions are generally performed in
anhydrous condition, the present approach of using hydrophobic
pocket as molecular vessel to perform dehydration reaction in
aqueous medium under mild reaction condition is quite
interesting. Moreover, the nano-confinement effect in promoting
the otherwise unfavorable dehydration reactions in water was
reflected from the poor or no yield of the dehydrated cyclized
xanthenes or non-cyclized tetraketones in absence of the cage
under similar reaction conditions. Due to the presence of AIE
active TPE moiety, the hexafluorophosphate salt of the
molecular barrel A showed aggregation induced emission
enhancement in acetonitrile upon addition of water. Surprisingly,
the nitrate analogue of the same barrel is soluble in water and
didn’t show any AIE activity.
1
1041, 1005, 958, 807, 760, 656, 514 cm- . ESI-MS (m/z): 1476.66
3
4
5
+
+
[A(PF6)9] , 1071.26 [A(PF6)8] + and 828.21 [A(PF6)7] .
General procedure for the synthesis of non-cyclized intermediate
Tetraone system (3a-3n):
Aldehyde 1 (0.02 mmol) and cyclic 1,3-diketones 2 (0.04 mmol) were
added to 1 mL aqueous solution of 5 mol% of catalyst A and the reaction
mixture was stirred at r.t. for respective time periods (Table 2). The
progress of the reaction was monitored by thin layer chromatography
(TLC). After completion of the reaction (monitored by disappearance of
the starting material in the TLC), the reaction mixture was extracted with
chloroform. The solvents were evaporated in a rotary evaporator and the
products were characterized by standard analytical techniques such as
(1H & 13C) NMR, FTIR, melting point determination, ESI-MS, X-ray
crystallographic analysis and all gave satisfactory results (Supporting
Information).
General procedure for the synthesis of cyclized Xanthene system
(4a-4o):
Aldehyde 1 (0.02 mmol) and cyclic 1,3-diketones 2 (0.04 mmol) were
added to 1 mL aqueous solution of 5 mol% of catalyst A and the reaction
mixture was heated at 60 °C for respective time periods (Table 3). The
progress of the reaction was monitored by thin layer chromatography
(TLC). After completion of the reaction (monitored by disappearance of
the starting material in the TLC), the reaction mixture was extracted with
chloroform. The solvents were evaporated in a rotary evaporator and the
products were characterized by standard analytical techniques such as
(1H & 13C) NMR, FTIR, melting point determination, ESI-MS, X-ray
crystallographic analysis and all gave satisfactory results (Supporting
Information).
EXPERIMENTAL SECTION
Materials and Methods
All the reagents were purchased from different commercial sources and
used without further purification. NMR (1D and 2D) spectra were recorded
on Bruker 400 MHz spectrometer and the chemical shifts (δ) in the 1H
NMR spectra are reported in ppm relative to tetramethylsilane (Me4Si) as
an internal standard (0.0 ppm) or proton resonance resulting from
incomplete deuteration of the solvents CDCl3 (7.26 ppm) and D2O (4.79
ppm). Electrospray ionization mass spectrometry (ESI-MS) experiments
were carried out on a Bruker Daltonics (Esquire 300 Plus ESI model)
spectrometer using standard spectroscopic-grade solvents. IR spectra
were recorded on a Bruker ALPHA FT-IR spectrometer. Analab μ–
ThermoCal10 instrument was used for melting point determinatuin. UV-
Visible and fluorescence spectra were recorded in Perkin Elmer Lambda-
750 and Horiba Jobin Yvon fluoromax4 spectrophotometers, respectively.
Quinine sulfate in 0.1 M H2SO4 was used to determine the experimental
quantum yields at an excitation wavelength of 365 nm with Φ = 0.56 for all
assemblies. The quantum yield measurements were performed in
multiplicates with values that were within 10 % error being averaged. The
absolute fluorescence quantum yields were measured by Quanta-f
Horiba instrument. Transmission electron microscopy was performed on
a JEOL JEM-2100F instrument operating at 200 kV Dynamic light
scattering (DLS) measurements were performed on the zetaseizer
instrument ZEN3600 (Malvern, UK) with a 1738 back scattering angle and
He-Ne laser (l=633 nm).
Acknowledgements
P.S.M. is grateful to DST-India for financial (EMR/2015/002353)
support. P.D. is grateful to UGC (New Delhi) for the Dr. D. S.
Kothari postdoctoral fellowship. P.H. thanks Bristol Mayer Squibb
for fellowship.
Keywords: Self-assembly
• Supramolecular • Coordination
architectures • Cage compounds • Palladium(II)
[1] (a) P. J. Stang, B. Olenyuk, Acc. Chem. Res. 1997, 30, 502-518; b) S.
Leininger, B. Olenyuk, P. J. Stang, Chem. Rev. 2000, 100, 853-908;
c) B. J. Holliday, C. A. Mirkin, Angew. Chem. Int. Ed. 2001, 40,
2022-2043; Angew. Chem. 2001, 113, 2076-2097; d) S. R. Seidel, P.
J. Stang, Acc. Chem. Res. 2002, 35, 972-983; e) M. Fujita, M.
Tominaga, A. Hori, B. Terrien, Acc. Chem. Res. 2005, 38, 369-378; f)
C. G. Oliver, P. A. Ulman, M. J. Wiester, C. A. Mirkin, Acc. Chem.
Res. 2008, 41, 1618-1629; g) M. J. Parkash, M. S. Lah, Chem.
Commun. 2009, 3326-3341; h) K. Ghosh, H.-B. Yang, B. H. Northrop,
M. M. Lyndon, Y.-R. Zheng, D. C. Muddiman, P. J. Stang, J. Am.
This article is protected by copyright. All rights reserved.

10.1002/chem.201702263
Chemistry - A European Journal
FULL PAPER
Chem. Soc. 2008, 130, 5320-5334; i) K. Ghosh, J.-M.Hu, H. S.White,
P. J. Stang, J. Am. Chem. Soc. 2009, 131, 6695-6697; j) J. Vacek,
D. C. Caskey, D. Horinek, R. K. Shoemaker, P. J. Stang, J. Michl, J.
Am. Chem. Soc. 2008, 130, 7629-7638; k) M. D. Pluth, R. G.
Bergman, K. N. Raymond, J. Am. Chem. Soc. 2008, 130, 11423-
11429; l) J. S. Mugridge, R. G. Bergman, K. N. Raymond, J. Am.
Chem. Soc. 2010, 132, 1182-1183; m) S. Shanmugaraju, P. S.
Mukherjee, Chem. Commun. 2015, 51, 16014-16032.
Am. Chem. Soc. 2010, 132, 16873-16882; d) D. Samanta, P. S.
Mukherjee, Chem. Commun. 2013, 49, 4307-4309; e) T. K. Ronson,
B. S. Pilgrim, J. R. Nitschke, J. Am. Chem. Soc. 2016, 138, 10417-
10420; f) W. Brenner, T. K. Ronson, J. R. Nitschke, J. Am. Chem.
Soc. 2017, 139, 75-78; g) Z. J. Wang, C. J. Brown, R. G. Bergman,
K. N. Raymond, F. D. Toste, J. Am. Chem. Soc. 2011, 133, 7358-
7360; h) M. D. Pluth, R. G. Bergman, K. N. Raymond, Science 2007,
85-88; i) S. Wang, T. Sawada, M. Fujita, Chem. Commun. 2016, 52,
11653-11656; j) M. Schmittel, B. He, P. Mal, Org. Lett. 2008, 10,
2513-2516; k) M. Schmittel, K. Mahata, Inorg. Chem. 2009, 48, 822-
824.
[2] a) M. Fujita, M. Tominaga, A. Hori, B. Therrien, Acc. Chem. Res. 2005,
38, 369-378; b) J. R. Nitschke, Acc. Chem. Res. 2006, 40, 103-112;
c) M. D. Pluth, K. N. Raymond, Chem. Soc. Rev. 2007, 36, 161-171;
d) S. Liu, Y.-F. Han, G.-X. Jin, Chem. Soc. Rev. 2007, 36, 1543-1560;
e) A. H. Clever, M. Shionoya, Coord. Chem. Rev. 2010, 254, 2391-
2402; f) R. Chakrabarty, P. S. Mukherjee, P. J. Stang, Chem. Rev.
2011, 111, 6810-6918; g) Y. Takezawa, M. Shionoya, Acc. Chem.
Res. 2012, 45, 2066-2076; h) T. R. Cook, Y. Zheng, P. J. Stang,
Chem. Rev. 2013, 113, 734-777; i) A. Castilla, W. Ramsay, J. R.
Nitschke, Acc. Chem. Res. 2014, 47, 2063-2073; j) M. Han, D. M.
Engelhard, G. H. Clever, Chem. Soc. Rev. 2014, 43, 1848-1860; k)
Y.-F. Han, G.-X. Jin, Acc. Chem. Res. 2014, 47, 3571-3579; l) M.
Yoshizawa, J. K. Klosterman, Chem. Soc. Rev. 2014, 43, 1885-1898;
m) M. Fujita, J. Yazaki, K. Ogura, J. Am. Chem. Soc. 1990, 112,
5645-5647; n) P. J. Stang, D. H. Cao, J. Am. Chem. Soc. 1994, 116,
4981-4982; o) M. Fujita, D. Oguro, M. Miyazawa, H. Oka, K.
Yamaguchi, K. Ogura, Nature 1995, 378, 469-471.
[3] a) B. Olenyuk, M. D. Levin, J. A. Whiteford, J. E. Shield, P. J. Stang, J.
Am. Chem. Soc. 1999, 121, 10434-10435; b) B. Olenyuk, J. A.
Whiteford, A. Fechtenkotter, P. J. Stang, Nature 1999, 398, 796-799;
c) S. J. Lee, W. Lin, J. Am. Chem. Soc. 2002, 124, 4554-4555; d)
C. J. Kuehl, Y. K. Kryschenko, U. Radhakrishnan, S. R. Seidel, S. D.
Huang, P. J. Stang, Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4932-
4936; e) A. M. Brown, M. V. Ovchinnikov, C. L. Stern, C. A. Mirkin, J.
Am. Chem. Soc. 2004, 126, 14316-14317; f) K. Nakabayashi, M.
Kawano, M. Yoshizawa, S. Ohkoshi, M. Fujita, J. Am. Chem. Soc.
2004, 126, 16694-16695; g) P. Wang, C. N. Moorefield, G. R.
Newkome, Angew. Chem. Int. Ed. 2005, 44, 1679-1683; Angew.
Chem. 2005, 117, 1707-1711; h) J. Heo, C. A. Mirkin, Angew. Chem.
Int. Ed. 2006, 45, 941-944; Angew. Chem. 2006, 118, 955-958; i) V.
M. Dong, D. Fiedler, B. Carl, R. G. Bergman, K. N. Raymond, J. Am.
Chem. Soc. 2006, 128, 14464-14465; j) K. Harano, S. Hiraoka, M.
Shionoya, J. Am. Chem. Soc. 2007, 129, 5300-5301; k) A. K. Bar,
R. Chakrabarty, G. Mostafa, P. S. Mukherjee, Angew. Chem., Int. Ed.
2008, 47, 8455-8459; l) W. Meng, J. K. Clegg, J. D. Thoburn, J. R.
Nitschke, J. Am. Chem. Soc. 2011, 133, 13652-13660; m) G. H.
Clever, W. Kawamura, S. Tashiro, M. Shiro, M. Shionoya, Angew.
Chem. Int. Ed. 2012, 51, 2602-2605; Angew. Chem. 2012, 124,
2656-2659; n) M. Wang, C. Wang, X.-Q. Hao, X. Li, T. J. Vaughn, Y.-
Y. Zhang, Y. Yu, Z.-Y. Li, M.-P. Song, H.-B. Yang, X. Li, J. Am. Chem.
Soc. 2014, 136, 10499-10507; o) C. S. Wood, T. K. Ronson, A. M.
Belenguer, J. J. Holstein, J. R. Nitschke, Nat. Chem. 2015, 7, 354-
358.
[8] a) D. Samanta, S. Mukherjee, Y. P. Patil, P. S. Mukherjee, Chem. Eur. J.
2012, 18, 12322-12329; b) P. Wei, X. Yan, F. Huang, Chem. Soc.
Rev. 2015, 44, 815-832; c) X.-Y. Hu, T. Xiao, C. Lin, F. Huang, L.
Wang, Acc. Chem. Res. 2014, 47, 2041-2051; d) P. Wei, T. R.Cook,
X. Yan, F. Huang, P. J. Stang, J. Am. Chem. Soc. 2014, 136, 15497-
15500; e) X. Ji, J. Chen, X. Chi, F. Huang, ACS Macro Lett. 2014, 3,
110-113; f) D. Xia, G. Yu, J. Li, F. Huang, Chem. Commun. 2014, 50,
3606-3608; g) X. Yan, B. Jiang, T. R. Cook, Y. Zhang, J. Li, Y. Yu,
F. Huang, H.-B. Yang, P. J. Stang, J. Am. Chem. Soc. 2013, 135,
16813-16816; h) X. Yan, S. Li, T. R. Cook, X. Ji, Y. Yao, J. B.
Pollock, Y. Shi, G. Yu, J. Li, F. Huang, P. J. Stang, J. Am. Chem.
Soc. 2013, 135, 14036-14039; i) Y. Li, Z. Jiang, M.Wang, J.Yuan, D.
Liu, X. Yang, M. Chen, J. Li, X. Yan, P. Wang, J. Am. Chem. Soc.
2016, 138, 10041-10046; j) M. Wang, K. Wang, C. Wang, M. Huang,
X.–Q. Hao, M.–Z. Shen, G.–Q. Shi, Z. Zhang, B. Song, A. Cisneros,
M.–P. Song, B. Xu, X. Li, J. Am. Chem. Soc. 2016, 138, 9258-
9268; k) W. Zheng, L.–J. Chen, G. Yang, B. Sun, X. Wang, B. Jiang,
G.–Q. Yin, L. Zhang, X. Li, M. Liu, G. Chen, H.–B. Yang, J. Am.
Chem. Soc. 2016, 138, 4927-4937; l) B. Sun, M. Wang, Z. Lou, M.
Huang, C.Xu, X. Li, L.–J.Chen, Y.Yu, G. L.Davis, B.Xu, H.–B.Yang,
X. Li, J. Am. Chem. Soc. 2015, 137, 1556-1564; m) X. Lu, X. Li, Y.
Cao, A. Schultz, J.–L. Wang, C. N. Moorefield, C. S. Wesdemiotis, Z.
D. Cheng, G. R. Newkome, Angew. Chem. Int. Ed. 2013, 52, 7728-
7731; Angew. Chem. 2013, 125, 7882-7885; n) B. Song, Z.Zhang, K.
Wang, C.–H. Hsu, O. Bolarinwa, J. Wang, Y. Li, G.–Q. Yin, E. Rivera,
H.–B. Yang, C. Liu, B. Xu, X. Li, Angew. Chem. Int. Ed. 2017, 56,
5258-5262; Angew. Chem. 2017, 129, 5342-5346; o) A. M. Johnson,
M. C. Young, X. Zhang, R. R. Julian, R. J. Hooley, J. Am. Chem. Soc.
2013, 135, 17723-17726; p) L. R. Holloway, H. H. McGarraugh, M. C.
Young, W. Sontising, G. J. O. Beran, R. J. Hooley, Chem. Sci. 2016,
7, 4423-4427; q) C. A. Wiley, L. R. Holloway, T. F. Miller, Y. Lyon, R.
R. Julian, R. J. Hooley, Inorg. Chem. 2016, 55, 9805-9815; r) A. M.
Johnson, R. J. Hooley, Inorg. Chem. 2011, 50, 4671-4673; s) A. M.
Johnson, O. Moshe, A. S. Gamboa, B. W. Langloss, J. F. K. Limtiaco,
C. K.Larive, R.J. Hooley, Inorg. Chem. 2011, 50, 9430-9442.
[9] a) B.; Smit, T. L. M. Maesen, Nature 2008, 451, 671-678; b) O.
Seneque, M. N. Rager, M. Giorgi, O. Reinaud, J. Am. Chem. Soc.
2000, 122, 6183-6189; c) H. Takezawa, T. Murase, M. Fujita, J. Am.
Chem. Soc. 2012, 134, 17420-17423; d) K. Jie, M. Liu, Y.Zhou, M.A.
Little, S.Bonakala, S. Y.Chong, A. Stephenson, L. Chen, F. Huang, A.
I. Cooper, J. Am. Chem. Soc. 2017, 139, 2908-2911; e) P. Liao, B.
W. Langloss, A. M. Johnson, E. R. Knudsen, F. S. Tham, R. R. Julian,
R. J. Hooley, Chem. Commun. 2010, 46, 4932-4934; f) P. S.
Mukherjee, K. S. Min, A. M. Arif, P. J. Stang, Inorg. Chem. 2004, 43,
6345-6350..
[4] a) Y. Yamanoi, Y. Sakamoto, T. Kusukawa, M. Fujita, S. Sakamoto, K.
Yamaguchi, J. Am. Chem. Soc. 2001, 123, 980-981; b) T. Nakamura,
H. Ube, R. Miyake, M. Shionoya, J. Am. Chem. Soc. 2013, 135,
18790-18793; c) I. A. Riddell, Y. R. Hristova, J. K. Clegg, C. S.Wood,
B. Breiner, J. R. Nitschke, J. Am. Chem. Soc. 2013, 135, 2723-2729.
[5] a) T. S. Koblenz, J. Wassenaar, J. N. H. Reek, Chem. Soc. Rev. 2008,
37, 247-262; b) M. Mastalerz, I. M. Oppel, Angew. Chem. Int. Ed.
2012, 51, 5252-5255; Angew. Chem. 2012, 124, 5345-5348.
[6] a) K. Ono, M. Yoshizawa, T. Kato, M. Fujita, Chem. Commun. 2008,
2328-2330; b) J. Lee, K. Ghosh, P. J. Stang, J. Am. Chem. Soc.
2009, 131, 12028-12029; c) D. Samanta, S. Shanmugaraju, S. A.
Joshi, Y. P. Patil, M. Nethaji, P. S. Mukherjee, Chem. Commun.
2012, 48, 2298-2300; d) A. K. Bar, S. Raghothama, D. Moon, P. S.
Mukherjee, Chem.–Eur. J. 2012, 18, 3199-3209.
[10] Y.Inokuma, M.; Kawano, M. Fujita, Nat. Chem. 2011, 3, 349-358.
[11] a) M. R. Ghadiri, J. R. Granja, L. K. Buehler, Nature 1994, 369, 301-
304; b) K. Motesharei, M. R. Ghadiri, J. Am. Chem. Soc. 1997, 119,
11306-11312; c) M. Engels, D. Bashford, M. R. Ghadiri, J. Am.
Chem. Soc. 1995, 117, 9151-9158; d) W. Yuan, T. Friscic, D.
Apperley, S. L. James, Angew. Chem. Int. Ed. 2010, 49, 3916-3919;
Angew. Chem. 2010, 122, 4008-4011; e) A. Corma, Chem. Rev.
1997, 97, 2373-2420; f) W. Meng, B. Breiner, K. Rissanen, J. D.
Thoburn, J. K. Clegg, J. R. Nitschke, Angew. Chem. Int. Ed. 2011,
50, 3479-3483; Angew. Chem. 2011, 123, 3541-3545; g) R. Wyler, J.
de Mendoza, J. Jr. Rebek, Angew. Chem. Int. Ed. 1993, 32, 1699-
1701; Angew. Chem. 1993, 105, 1820-1821; h) G. Yu, G. Tang, F.
Huang, J. Mater. Chem. C 2014, 2, 6609-6617; i) G. Yu, Y. Ma, C.
[7] a) Z. Zhao, Y.-R. Zheng, M. Wang, J. B. Pollock, P. J. Stang, Inorg.
Chem. 2010, 49, 8653-8655; b) M. Wang, Y.-R. Zheng, K. Ghosh, P.
J. Stang, J. Am. Chem. Soc. 2010, 132, 6282-6283; c) Y.-R. Zheng,
Z.Zhao, M.Wang, K.Ghosh, J. B. Pollock, T. R. Cook, P. J. Stang, J.
This article is protected by copyright. All rights reserved.

10.1002/chem.201702263
Chemistry - A European Journal
FULL PAPER
Han, Y. Yao, G. Tang, Z. Mao, C. Gao, F. Huang, J. Am. Chem. Soc.
2013, 135, 10310-10313; j) K. Jie, Y. Zhou, Y. Yao, B. Shi, F. Huang,
J. Am. Chem. Soc. 2015, 137, 10472-10475; k) M. Zhang, M. L.
Saha, M. Wang, Z. Zhou, B. Song, C. Lu, X. Yan, X. Li, F. Huang, S.
Yin, P. J. Stang, J. Am. Chem. Soc. 2017, 139, 5067-5074; l) S.
Dong, Y. Luo, X. Yan, B. Zheng, X. Ding, Y. Yu, Z. Ma, Q. Zhao, F.
Huang, Angew. Chem. Int. Ed. 2011, 50, 1905-1909; Angew. Chem.
2011, 123, 1945-1949; m) B. Jiang, J. Zhang, J.–Q. Ma, W. Zheng,
L.–J.Chen, B. Sun, C.Li, B.–W. Hu, H. Tan, X. Li, H.–B. Yang, J. Am.
Chem. Soc. 2016, 138, 738-741; n) Y. Liu, L. Perez, M. Mettry, C. J.
Easley, R. J. Hooley, W. Zhong, J. Am. Chem. Soc. 2016, 138,
10746-10749; o) S. Ghosh, D. R. Turner, S. R. Batten, P. S. Mukherjee,
Dalton. Trans. 2007, 1869-1871; p) L. R. Holloway, H. H. McGarraugh,
M. C. Young, W. Sontising, G. J. O. Beran, R. J. Hooley, Chem. Sci.
2016, 7, 4423-4427.
Int. Ed. Engl., 2001, 44, 6748-6751; Angew. Chem. 2004, 116, 6916-
6919; d) Q. Zhang, K. Tiefenbacher, J. Am. Chem. Soc. 2013, 135,
16213-16219; e) W. M. Hart-Cooper, K. Clary, F. D. Toste, R. G.
Bergman, K. N. Raymond, J. Am. Chem. Soc. 2012, 134, 17873-
17876.
[21] C.-J.Li, L. Chen, Chem. Soc. Rev. 2006, 35, 68-82.
[22] a) Y. Liu, Y. Tang, N. N. Barashkov, I. S. Irgibaeva, J. W. Y.Lam, R. R.
Hu, D. Birimzhanova, Y. Yu, B. Z. Tang, J. Am. Chem. Soc. 2010,
132, 13951-13953; b) K. Kim, O. G. Tsay, D. A. Atwood, D. G.
Churchill, Chem. Rev. 2011, 111, 5345-5403; c) L.-Y. Niu, Y.-S.Guan,
Y.-Z. Chen, L.-Z. Wu, C.-H. Tung, Q.-Z. Yang, J. Am. Chem. Soc.
2012, 134, 18928-18931; d) H. Zhu, J. Fan, B. Wang, X. Peng, Chem.
Soc. Rev. 2015, 44, 4337-4366; e) J.-X. Wang, Q. Chen, N. Bian, F.
Yang, A.-D. Qi, C.-G. Yan, B.-H. Han, Org. Biom. Chem. 2011, 9,
2219-2226.
[12] a) J.-M. Lehn, Supramolecular Chemistry, Weinheim, 1995; b) J.
Rebek, Acc. Chem. Res. 1999, 32, 278-286; c) J. P. Sauvage, Acc.
Chem. Res. 1998, 31, 611-619; d) D. L. Caulder, K. N. Raymond, J.
Chem. Soc. Dalton Trans. 1999, 1185-1200; e) J. M. Kang, J. J.
Rebek, Nature 1997, 385, 50-52; f) M. Kuil, T. Soltner, P. W. N. M.
van Leeuwen, J. N. H. Reek, J. Am. Chem. Soc. 2006, 128, 11344-
11345; g) J.-L. Hou, D. Ajami, J. Jr. Rebek, J. Am. Chem. Soc. 2008,
130, 7810-7811; h) C. J. Hastings, M. P. Backlund, R. G. Bergman,
K. N. Raymond, Angew. Chem. Int. Ed. 2011, 50, 10570-10573;
Angew. Chem. 2011, 123, 10758-10761.
[13] a) M. Fujita, N. Fujita, K. Ogura, K. Yamaguchi, Nature 1999, 400, 52-
55; b) M. Ziegler, J. L. Brumaghim, K. N. Raymond, Angew. Chem.
Int. Ed. 2000, 39, 4119-4121; Angew. Chem. 2000, 112, 4285-4287;
c) M. Ziegler, J. L. Brumaghim, K. N. Raymond, Angew. Chem. Int.
Ed. 2000, 39, 4119-4121; Angew. Chem. 2000, 39, 4119-4121; d)
M. Yoshizawa, Y. Takeyama, T. Okano, M. Fujita, J. Am. Chem. Soc.
2003, 125, 3243-3247; e) M. Fujita, K. Umemoto, M. Yoshizawa, N.
Fujita, T. Kusukawa, Chem. Commun. 2001, 509-518; f) M.
Yoshizawa, M. Tamura, M. Fujita, Science 2006, 312, 251-514; g) T.
Iwasawa, R. J. Hooley, J. Jr. Rebek, Science 2007, 317, 493-496; h)
Z. J. Wang, K. N. Clary, R. G. Bergman, K. N. Raymond, F. D. Toste,
Nat. Chem. 2013, 5, 100-103; i) D. H. Leung, D. Fiedler, R. G.
Bergman, K. N. Raymond, Angew. Chem. Int. Ed. 2004, 43, 963-966;
Angew. Chem.2004, 116, 981-984; j) D. H. Leung, R. G.Bergman, K.
N. Raymond, J. Am. Chem. Soc. 2006, 128, 9781-9797.
[23] a) M. Zhu, C. Yang, Chem. Soc. Rev. 2013, 42, 4963-4976; b) X. Dai,
Z. Zhang, Y. Jin, Y. Niu, H. Cao, X. Liang, L. Chen, J. Wang, X. Peng,
Nature 2014, 515, 96-99; c) A. C. Grimsdale, K. Leok Chan, R. E.
Martin, P. G. Jokisz, A. B. Holmes, Chem. Rev. 2009, 109, 897-1091;
d) I. D. W. Samuel, G. A. Turnbull, Chem. Rev. 2007, 107, 1272-
1295; e) J. Kido, Y. Okamoto, Chem. Rev. 2002, 102, 2357-2368; f)
A. Kohler, J. S. Wilson, R. H. Friend, Adv. Mater. 2002, 14, 701-707;
g) G. M.Farinola, R. Ragni, Chem. Soc. Rev. 2011, 40, 3467-3482.
[24] a) L. Maggini, D. Bonifazi, Chem. Soc. Rev. 2012, 41, 211-241; b) Z.
Zhang, K.Guo, Y.Li, X.Li, G.Guan, H.Li, Y.Luo, F.Zhao, Q.Zhang, B.
Wei, Q.Pei, H. Peng, Nat. Photonics 2015, 9, 233-238.
[25] S. K. Yang, Nature Chem. 2013, 5, 692-697.
[26] a) J. B. Birks, Photophysics of Aromatic Molecules; Wiley: London,
1970. b) C.-T. Chen, Chem. Mater. 2004, 16, 4389-4400; c) R. H.
Friend, R. W. Gymer, A. B. Holms, J. H. Burroughes, R. N. Marks, C.
D. Taliani, D. C. Bradley, D. A. Dos Santos, J. L. Brédas, M.Lögdlund,
W. R. Salaneck, Nature 1999, 397, 121-128; d) C. W. Tang, S. A.
Vanslyke, Appl. Phys. Lett. 1987, 51, 913-915; e) E. A. Jares-
Erijman, T. M. Jovin, Nat. Biotechnol. 2003, 21, 1387-1395.
[27] a) J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S.Kwok,
X. Zhan, Y. Liu, D. Zhu, B. Z. Tang, Chem. Commun. 2001, 1740-
1741; b) J. Mei, Y. Hong, J. W. Y. Lam, A. Qin, Y. Tang, B. Z. Tang,
Adv. Mater. 2014, 26, 5429-5479; c) J. Mei, N. L. C. Leung, R. T. K.
Kwok, J. W. Y. Lam, B. Z. Tang, Chem. Rev. 2015, 115, 11718-
11940.
[14] a) J. M. Kang, G. Hilmersson, J. Santamaria, J. Am. Chem. Soc.
1998, 120, 3650-3656; b) J. Chen, J. Jr. Rebek, Org. Lett. 2002, 4,
327-329; c) T. Heinz, D. Rudkevich, J. Jr. Rebek, Angew. Chem. Int.
Ed. 1999, 38, 1136-1139; Angew. Chem. 1999, 111, 1206-1209; d)
C. J. Brown, F. D. Toste, R. G. Bergman, K. N. Raymond, Chem.
Rev. 2015, 115, 3012-3035; e) F. Hof, S. L. Craig, C. J. R. Nuckolls,
Angew. Chem. Int. Ed. 2002, 41, 1488-1508; Angew. Chem. 2002,
114, 1556-1578; f) T. S. Koblenz, J. Wassenaar, J. N. H. Reek,
Chem. Soc. Rev. 2008, 37, 247-262; g) M. Yoshizawa, J. K.
Klosterman, M. Fujita, Angew. Chem. Int. Ed. 2009, 48, 3418-3438;
Angew. Chem. 2009, 121, 3470-3490; h) M. Marty, Z. C. Watson, L.
J. Twyman, M. Nakash, J. K. M. Sanders, Chem. Commun. 1998,
2265-2266.
[28] a) Aggregation-Induced Emission: Applications (Eds: B. Z. Tang, A.
Qin), Wiley, Hoboken, 2013; b) Y. Hong, J. W. Y. Lam, B. Z. Tang,
Chem. Soc. Rev. 2011, 40, 5361-5388; c) J. Huang, N. Sun, J.Yang,
R. Tang, Q. Li, D. Ma, J. Qin, Z. Li, J. Mater. Chem. 2012, 22, 12001-
12007; d) C.W. T. Leung, Y. Hong, S. Chen, E. Zhao, J. W. Y. Lam,
B. Z. Tang, J. Am. Chem. Soc. 2013, 135, 62-65; e) E. Q. Procopio,
M.Mauro, M.Panigati, D.Donghi, P.Mercandelli, A.Sironi, G.D lfonso,
L. D. Cola, J. Am. Chem. Soc. 2010, 132, 14397-14399; f) W. Z.
Yuan, P. Lu, S. Chen, J. W. Y. Lam, Z. Wang, Y. Liu, H. S. Kwok, Y.
Ma, B. Z. Tang, Adv. Mater. 2010, 22, 2159-2163; g) H.Shi, J.Liu, J.
Geng, B. Z.Tang, B. Liu, J. Am. Chem. Soc. 2012, 134, 9569-9572.
[29] a) X. Yan, T. R. Cook, P. Wang, F. Huang, P. J. Stang, Nat. Chem.
2015, 7, 342-348; b) X. Yan, H. Wang, C. E. Hauke, T. R. Cook, M.
Wang, M. L. Saha, Z. Zhou, M. Zhang, X. Li, F. Huang, P. J. Stang, J.
Am. Chem. Soc. 2015, 137, 15276-15286.
[30] a) X. Yan, M. Wang, T. R. Cook, M. Zhang, M. L. Saha, Z. Zhou, X. Li,
F. Huang, P. J. Stang, J. Am. Chem. Soc. 2016, 138, 4580-4588; b)
Y. Tian, X. Yan, M. L. Saha, Z. Niu, P. J. Stang, J. Am. Chem. Soc.
2016, 138, 12033-12036; c) M. Zhanga, S. Lib, X. Yana, Z. Zhoua, M.
L. Saha, Y.-C. Wang, P. J. Stang, Proc. Natl. Acad. Sci. U. S. A.
2016, 113, 11100-11105.
[15] J. Kang, J. Santamaría, G. Hilmersson, Jr. J. Rebek, J. Am. Chem.
Soc. 1998, 120, 7389-7390.
[16] M. L. Merlau, M. P. Mejia, S. T. Nguyen, J. T. Hupp, Angew. Chem.
Int. Ed. Engl., 2001, 40, 4239-4242; Angew. Chem. 2001, 113, 4369-
4372.
[17] D. Fiedler, R. G. Bergman, K. N. Raymond, Angew. Chem. Int. Ed.
Engl. 2004, 43, 6748-6751; Angew. Chem. 2004, 116, 6916-6919.
[18] a) T. Murase, Y. Nishijima, M. Fujita, J. Am. Chem. Soc. 2011, 134,
162-164; b) T. Murase, Y. Nishijima, M. Fujita, J. Am. Chem. Soc.
2012, 134, 162-164.
[19] C. J. Hastings, M. D. Pluth, R. G. Bergman, K. N. Raymond, J. Am.
Chem. Soc. 2010, 132, 6938-6940.
[20] a) Y. Nishioka, T. Yamaguchi, M. Kawano, M. Fujita, J. Am. Chem.
Soc. 2008, 130, 8160-8161; b) M. Yoshizawa, T. Kusukawa, M. Fujita,
S. Sakamoto, K. Yamaguchi, J. Am. Chem. Soc. 2001, 123, 10454-
10459; c) D. Fiedler, R. G. Bergman, K. N. Raymond, Angew. Chem.
[31] a) H. Li, J. Fan, X. Peng, Chem. Soc. Rev. 2013, 42, 7943-7962; b)
H. Li, J. Fan, J. Du, K. Guo, S. Sun, X. Liu, X. Peng, Chem. Commun.
2010, 46, 1079-1081; c) B. Liu, Y. Bao, F. Du, H. Wang, J. Tian, R.
Bai, Chem. Commun. 2011, 47, 1731-1733; d) B. K. Pal, M. S.
Rahman, Mikrochim. Acta, 1999, 131, 139-144; e) B. Liu, Y. Bao, H.
Wang, F. Du, J. Tian, Q. Li, T. Wang, R. Bai, J. Mater. Chem. 2012,
22, 3555-3561; f) E. Unterreitmaier, M. Schuster, Anal. Chim. Acta,
1995, 309, 339-341; g) K. Kubo, Y. Miyazaki, K. Akutso, T. Sakurai,
This article is protected by copyright. All rights reserved.

10.1002/chem.201702263
Chemistry - A European Journal
FULL PAPER
Heterocycles 1999, 51, 965-968; h) Y. J. Fang, H. Chen, Z. X. Gao,
X. Y. Jin, Indian J. Chem., Sect. A 2002, 41, 521; i) L. P. Duan, Y.
F. Xu, X. H. Qian, Chem. Commun. 2008, 6339-6341; j) L. Fabbrizzi,
M. Licchelli, P. Pallavicini, A. Perotti, A. Taglietti, D. Sacchi, Chem.–
Eur. J. 1996, 2, 75-82.
2014, 136, 7241-7244; e) Q.Zhang, J.Su, D.Feng, Z.Wei, X.Zou, H.-
C. Zhou, J. Am. Chem. Soc. 2015, 137, 10064-10067.
[44] a) N. C. Gianneschi, M. S. Masar, C. A. Mirkin, Acc. Chem. Res. 2005,
38, 825-837; b) M. Fujita, Chem. Soc. Rev. 1998, 27, 417-425; c)
F. A. Cotton, C. Lin, C. A. Murillo, Acc. Chem. Res. 2001, 34, 759-
771; d) D. L. Caulder, K. N. Raymond, Acc. Chem. Res. 1999, 32,
975-982.
[32] K. Y. Kim, S. H. Jung, J.-H. Lee, S. S. Lee, J. H. Jung, Chem.
Commun. 2014, 50, 15243-15246.
[33] a) J. P. Poupelin, G. Saint-Ruf, O. Foussard-Blanpin, G. Narcisse, G.
Uchida-Ernouf, R. Lacroix, Eur. J. Med. Chem. 1978, 13, 67-71; b)
G. Saint-Ruf, A. De, H. T. Hieu, Bull. Chim. Ther. 1972, 7, 83-86; c)
R. M. Ion, Prog. Catal. 1997, 2, 55-76; d) T. M. Ahmad, A. King, D.-
K. Ko, B. H. Cha, J. J. Lee, J. Phys.D: Appl. Phys. 2002, 35, 1473-
1476; e) C. G. Knight, T. Stephens, Biochem. J. 1989, 258, 683-
687; f) Q. Zhang, H. Su, J. Luo, Y. Wei, Green Chem. 2012, 14, 201-
208; g) P. Das, A. Dutta, A. Bhaumik, C. Mukhopadhyay, Green
Chem. 2014, 16, 1426-1435.
[45] Z. Zhou, X. Yan, M. L. Saha, M. Zhang, M. Wang, X. Li, P. J. Stang, J.
Am. Chem. Soc. 2016, 138, 13131-13134.
[34] a) P. Shanmugasundram, K. J. Prabahar, V. T. Ramakrishnan, J.
Heterocycl. Chem. 1993, 30, 1003-1007; b) P. Shanmugasundram, P.
Murugan, V. T. Ramakrishnan, N. Srividya, P. Ramamurthy,
Heteroatom Chem. 1996, 7, 17-22; c) K. J. Parabahar, K.
Rajagopalan, V. T. Ramakrishnan, Indian J. Chem. B 1989, 28, 952-
961; d) S. Ray, A. Bhaumik, M. Pramanik, R. J. Butcher, S. O.
Yildirimd, C. Mukhopadhyay, Catal. Commun. 2014, 43, 173-178.
[35] J. Qian, C. Klomsiri, M. W. Wright, S. B. King, A. W. Tsang, L. B. Pooleb,
C. M. Furdui, Chem. Commun. 2011, 47, 9203-9205.
[36] a) Z. Zhao, J. W. Y. Lam, B. Z. Tang, J. Mater. Chem. 2012, 22,
23726-23740; b) Y. Dong, J. W. Y. Lam, A. Qin, J. Liu, Z. Li, B. Z.
Tang, J. Sun, H. S. Kwok, Appl. Phys. Lett. 2007, 91, 011111-3; c)
A.Qin, C. K. W.Jim, Y.Tang, J. W. Y.Lam, J.Liu, F.Mahtab, P.Gao,
B. Z. Tang, J. Phys. Chem. B 2008, 112, 9281-9288; d) Y. Hong, J.
W. Y. Lam, B. Z. Tang, Chem. Commun. 2009, 4332-4353; e) V. S.
Vyas, R. Rathore, Chem. Commun. 2010, 46, 1065-1067.
[37]J. Shi, N.Chang, C. Li, J.Mei, C.Deng, X.Luo, Z. Liu, Z.Bo, Y. Q. Dong,
B. Z. Tang, Chem. Commun. 2012, 48, 10675-10677.
[38] a) G. Liang, J. W. Y. Lam, W. Qin, J. Li, N. Xie, B. Z. Tang, Chem.
Commun. 2014, 50, 1725-1727; b) P. Wang, X. Yan, F. Huang,
Chem. Commun. 2014, 50, 5017-5019; c) N. Song, D.-X. Chen, Y.-C.
Qiu, X.-Y. Yang, B. Xu, W. Tian, Y.-W. Yang, Chem. Commun. 2014,
50, 8231-8234; d) J. Wu, S. Sun, X. Feng, J. Shi, X.-Y. Hu, L. Wang,
Chem. Commun. 2014, 50, 9122-9125; e) W. Bai, Z. Wang, J. Tong,
J. Mei, A. Qin, J. Z. Sun, B. Z. Tang, Chem. Commun. 2015, 51,
1089-1091; f) L. He, X. Liu, J. Liang, Y. Cong, Z. Weng, W. Bu, Chem.
Commun. 2015, 51, 7148-7151.
[39] a) J. Zhao, D. Yang, Y. Zhao, X.-J. Yang, Y.-Y. Wang, B. Wu, Angew.
Chem. Int. Ed. 2014, 53, 6632-6636; Angew. Chem. 2014, 126,
6750-6754; b) F.Sun, G.Zhang, D.Zhang, L.Xue, H. Jiang, Org. Lett.
2011, 13, 6378-6381; c) S. Gui, Y. Huang, F. Hu, Y. Jin, G. Zhang, L.
Yan, D.Zhang, R. Zhao, Anal. Chem. 2015, 87, 1470-1474.
[40] a) H.-Q. Peng, J.-F. Xu, Y.-Z. Chen, L.-Z. Wu, C.-H. Tung, Q.-Z. Yang,
Chem. Commun. 2014, 50, 1334-1337; b) C. Zhang, Y. Li, X. Xue, P.
Chu, C.Liu, K.Yang, Y.Jiang, W.-Q.Chen, G.Zou, X.-J. Liang, Chem.
Commun. 2015, 51, 4168-4171; c) V. M. Suresh, A. De, T. K. Maji,
Chem. Commun. 2015, 51, 14678-14681.
[41] G.Yu, G.Tang, F. Huang, J. Mater. Chem. C 2014, 2, 6609-6617.
[42] a) L.Xu, L.Jiang, M.Drechsler, Y.Sun, Z.Liu, J.Huang, B. Z.Tang, Z.Li,
M. A. C. Stuart, Y. Yan, J. Am. Chem. Soc. 2014, 136, 1942-1947;
b) X. Liu, Y. Zeng, J. Liu, P. Li, D. Zhang, X. Zhang, T. Yu, J. Chen, G.
Yang, Y. Li, Langmuir 2015, 31, 4386-4393; c) L.-J. Chen, Y.-Y. Ren,
N.-W.Wu, B.Sun, J.-Q.Ma, L.Zhang, H.Tan, M.Liu, X.Li, H.-B. Yang,
J. Am. Chem. Soc. 2015, 137, 11725-11735.
[43] a) N. B. Shustova, B. D. McCarthy, M. inc , J. Am. Chem. Soc.
2011, 133, 20126-20129; b) N. B. Shustova, T.-C. Ong, A. F.
Cozzolino, V. K. Michaelis, R. G. Griffin, M. inc , J. Am. Chem.
Soc. 2012, 134, 15061-15070; c) Z. Wei, Z.-Y. Gu, R. K. Arvapally,
Y.-P.Chen, R. N., Jr.McDougald, J. F. Ivy, A. A.Yakovenko, D.Feng,
M. A. Omary, H.-C. Zhou, J. Am. Chem. Soc. 2014, 136, 8269-8276;
d) M. Zhang, G. Feng, Z. Song, Y.-P.Zhou, H.-Y.Chao, D. Yuan, T. T.
Y.Tan, Z.Guo, Z. Hu, B. Z.Tang, B. Liu, D. Zhao, J. Am. Chem. Soc.
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A water-soluble trigonal prism
Paramita Das, Atul Kumar,
was
synthesized.
The
Prodip Howlader, and Partha
Sarathi Mukherjee*
hydrophobic cavity of prism
was employed for selective
formation
tetraketones and xanthenes by
fine-tuning the reaction
of
intermediate
Page No. – Page No.
A Self-Assembled Trigonal
Prismatic Molecular Vessel
for Catalytic Dehydration
Reactions in Water
conditions in aqueous media.
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Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
Text for Table of Contents
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