Multifunctionalized porosity in zeolitic diamondoid porous organic salt: Selective adsorption and guest-responsive fluorescent properties

Article abstract of DOI:10.1016/j.tetlet.2012.12.086

An organic salt composed of triphenylmethylamine and a fluorescent disulfonic acid provides a diamondoid porous organic salt (d-POS) through formation of connectable tetrahedral supramolecular clusters. The d-POS completely keeps its open channel structure upon guest desorption and adsorption and shows not only zeolitic property such as selective gas and molecular adsorption but also tunable fluorescent property in response to adsorbed molecules. The fluorescent color is changed from blue to green by incorporating electron-donor molecules while the fluorescence is quenched by electron-acceptor molecules. These results demonstrate efficient usability of the design for constructing functional rigid porous structures.

Full text of DOI:10.1016/j.tetlet.2012.12.086

Tetrahedron Letters 54 (2013) 1268–1273
Contents lists available at SciVerse ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Multifunctionalized porosity in zeolitic diamondoid porous organic salt:
selective adsorption and guest-responsive fluorescent properties
Atsushi Yamamoto a, Tomofumi Hirukawa a, Ichiro Hisaki a, Mikiji Miyata a, Norimitsu Tohnai a,b,
⇑
a Department of Material and Life Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
b Japan Science and Technology Agency (JST), PRESTO 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
An organic salt composed of triphenylmethylamine and a fluorescent disulfonic acid provides a diamond-
oid porous organic salt (d-POS) through formation of connectable tetrahedral supramolecular clusters.
The d-POS completely keeps its open channel structure upon guest desorption and adsorption and shows
not only zeolitic property such as selective gas and molecular adsorption but also tunable fluorescent
property in response to adsorbed molecules. The fluorescent color is changed from blue to green by incor-
porating electron-donor molecules while the fluorescence is quenched by electron-acceptor molecules.
These results demonstrate efficient usability of the design for constructing functional rigid porous
structures.
Received 22 November 2012
Revised 16 December 2012
Accepted 21 December 2012
Available online 2 January 2013
Keywords:
Porous structure
Organic salt
Supramolecular cluster
Luminescence
Ó 2012 Elsevier Ltd. All rights reserved.
Diamondoid network
Non-covalently formed rigid porous materials1 have continu-
ously fascinated not only crystal engineering but also molecular
synthesis, material science, and other areas before the rapid grow-
ing of interest in metal organic frameworks (MOFs)2 and covalent
organic frameworks (COFs).3 Their rigid open channels cause uni-
form interactions between the host frameworks and adsorbates
to produce reproducible adsorption behaviors with small hystere-
sis.1c,d The rigidity also has significant roles in sorting the size and
shape of adsorbates.1h,2c,d Together with high thermal and chemi-
cal stability, which is essential for many practical uses, these char-
acteristics lead to widespread applications such as easy-to-use
storage and molecular separation. The porosity in these materials
is classified into two categories; ‘extrinsic porosity’ obtained by
lacunal molecular packing of small molecules such as tris(o-pheny-
lenedioxy)cyclophosphazene (TPP) and ‘intrinsic porosity’ derived
from covalently prefabricated shape-persistent cage compounds,
for example, calixarene derivatives.1g Recently, McKeown et al.
demonstrate some useful criteria to yield the extrinsic porosity
by using already-known potential compounds.1b,d However, it still
remains challenging to obtain desired structures and planned sta-
bilities owing to a complex set of weak intermolecular interac-
tions.4 Furthermore, non-covalent structures tend to be very
sensitive to minor molecular changes, which preclude interchange-
able identical design.
In this context, organic salts seem to be good candidates to
methodically regulate molecular arrangements.5 It has been best
investigated that guanidium sulfonates provide grid-type frame-
works based on continuous sheet-like hydrogen bonding syn-
thons.5a,b The robust synthons facilitate to yield predictable
structures and stabilities. In sharp contrast to these frameworks,
we recently reported that aromatic monosulfonic acids and triphe-
nylmethylamine (TPMA) hierarchically construct diamondoid por-
ous organic salts (d-POSs) (Fig. 1a).6 In the d-POSs, the organic salts
form discrete tetrahedral supramolecular clusters based on a
closed cubic-like hydrogen bonding synthon, which are succes-
sively cross-linked via p–p interactions between the monosulfonic
acids. Depending on sulfonic acids, the closed synthon gives more
significant structural diversity and freedom of the resultant frame-
works such as pore size and shape compared to the continuous
synthons. The d-POS system is a promising strategy to systemati-
cally regulate the pore size, shape, and flexibility by combining
appropriate linker of sulfonic acids.
Herein, we demonstrate rational and fascinating construction of
a novel zeolitic d-POS from an organic salt comprising fluorescent
disulfonic acid and TPMA (Figs. 1b and 2). The d-POS has not only
integrity upon guest desorption and adsorption but also fluores-
cent property to combine following functionalities; (i) efficient
gas adsorption with small hysteresis, (ii) molecular sieve effect
for gas and organic molecules, and (iii) fluorescent modulation in
response to various guest molecules. Hitherto, a variety of non-
covalent porous architecture has been fabricated. However, to
the best of our knowledge, this d-POS is the first report of
⇑
Corresponding author. Tel./fax: +81 6 6879 7404.
E-mail address: tohnai@mls.eng.osaka-u.ac.jp (N. Tohnai).
0040-4039/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2012.12.086

A. Yamamoto et al. / Tetrahedron Letters 54 (2013) 1268–1273
1269
Figure 1. Schematic representation of hierarchical construction of diamondoid porous organic salts (d-POSs) applying (a) monosulfonic acid and (b) disulfonic acid.
non-covalent structures combining permanent porosity and
guest-responsive fluorescent property. The present study proposes
a novel approach for designing functional rigid porous structures
toward potential applications beyond the conventional adsorption
properties.
The zeolitic d-POS was prepared from an organic salt 1 compris-
ing trans-stilbene-4,40-disulfonic acid (SBDS) and TPMA (Scheme 1).
Stilbene has been used as the fundamental unit of electro- and
photoluminescent conjugated polymer represented by poly
(p-phenylenevinylene) (PPV).7 Therefore, we expect that SBDS acts
as a strong but simple crosslinker as well as an emitter. The disul-
fonic acid and TPMA should form a connectable tetrahedral cluster
for a fluorescent rigid framework, leading to applications not only
in gas storage but also in sensors and tunable solid-state light-
emitting devices (Fig. 1b). The organic salt 1 was recrystallized
from methanol mixed with non-polar aromatic solvent such as tol-
uene and chlorobenzene to afford colorless block crystals. 1H NMR
measurements indicated that these crystals include the aromatic
solvents as guest molecules (Table S1). Interestingly, powder
X-ray diffraction (PXRD) measurements indicate that these crystals
have the same structures regardless of the inclusion species
(Fig. S1). To determine the molecular arrangement in detail, single
crystals suitable for X-ray crystallographic analysis were prepared
by recrystallization from a mixture of methanol and o-chlorotolu-
ene. The single crystal X-ray analysis revealed that SBDS and TPMA
construct a diamondoid porous organic salt, d-POS-1, including
o-chlorotoluene (d-POS-1ꢀCT, Fig. 2a and b) as expected.8 In
d-POS-1ꢀCT, four sulfonate anions and four ammonium cations
are assembled via charge-assisted hydrogen bonds to form a
connectable tetrahedral cluster with a cubic-like hydrogen bond
Scheme 1. Chemical structures of organic salt 1 and aromatic molecules used for
guest candidates.

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A. Yamamoto et al. / Tetrahedron Letters 54 (2013) 1268–1273
Figure 2. Crystal structure of the diamondoid porous organic salt including o-chlorotoluene (d-POS-1ꢀCT). (a) View along the c axis. Guest molecules of o-chlorotoluene are
omitted for clarity. Hydrogen atoms are omitted for clarity except in the space-filling model of a cluster. (b) Visualization of void space. In the sky-blue-colored void space,
guest molecules are represented by green balls and sticks. (c) Hierarchical interpretation of the host framework. In the diamondoid network and the 4-fold entangled host
framework, triphenylmethyl groups are omitted for clarity. The independent diamondoid networks are indicated by magenta, green, orange, and blue.
network (Fig. 2c). The neighboring sides of the clusters are approx-
imately 28 Å. Subsequently, the clusters are catenated by SBDS to
construct a robust diamondoid network possessing 43 ꢁ 34 Å hex-
agonal windows (Fig. 2c). Owing to its large void space, four inde-
pendent diamondoid networks are interpenetrated to yield an
entangled host framework with one-dimensional (1D) void space
(Fig. 2b and c). In the void space, three o-chlorotoluene molecules
are included per cluster. The void space has a bottleneck structure
with approximate maximum and minimum dimensions of
9.1 ꢁ 10.4 and 5.9 ꢁ 7.0 Å, respectively. The volume of the void
space is calculated by using PLATON/VOID9 to be 31.5% of the total
cell volume.
It should be noted that d-POS-1 has efficient stability on heating
and guest desorption. TGA data of d-POS-1ꢀCT show a gradual
weight loss of 16.3% up to 200 °C corresponding to desorption of
three o-chlorotoluene molecules per cluster (Fig. S2). Subse-
quently, second step following to large weight loss is observed over
235 °C, indicating decomposition of TPMA to break up the clusters.
Interestingly, this decomposition temperature is higher (35 °C)
than those of the flexible d-POSs reported in the previous litera-
ture.6 These results indicate that the way to connect the clusters
has significant influence on the thermal stability not only of the
resultant diamondoid networks but also of the components and
clusters themselves. X-ray analyses confirm that fully evacuated
framework d-POS-1 completely maintains its void space. As shown
in Figure 3a and b, the PXRD patterns display one sharp peak at
6.28 (d = 14.1 Å), corresponding to (110) plane of a distance be-
tween 1D void space, before and after guest desorption. Even after
guest desorption by heat treatment at 150 °C under reduced pres-
sure for 3 h, the crystals do not change physical appearance enough
to undergo single crystal X-ray analysis. The analysis revealed that
the cell parameters are almost equal within 1% differences be-
tween before and after the guest desorption (Table S2). Molecular
arrangement also does not make much difference except that the
vinyl group of SBDS rotates like paddle-wheel in d-POS-1 owing
to large free volume and absence of the guest molecules.8 Such
structural stability is distinctly different from the flexible d-POSs.
The flexible d-POSs applying monosulfonic acids cause large
shrinkage of their structures upon guest desorption to decrease
unoccupied void space.6 These results indicate that cross-linking
of the clusters via disulfonic acids is a simplistic and promising
universal strategy to improve low stability which organic porous
structures often confront with.
Gas adsorption measurements also prove to be the permanent
porosity. Figure 4 shows gas adsorption isotherms on d-POS-1
for three adsorbates. The adsorption of CO2 follows a typical
type-I isotherm at 194 K. Adsorption and desorption data show
no hysteresis and is nearly congruent, which indicate sufficient

A. Yamamoto et al. / Tetrahedron Letters 54 (2013) 1268–1273
1271
Moreover, d-POS-1 also reversibly adsorbs a variety of volatile
organic compounds (VOCs) such as toluene, chlorobenzene, and
xylene. d-POS-1ꢀCT was reproducibly obtained by exposing vacant
d-POS-1 to o-chlorotoluene vapor at 25 °C. TGA data of d-POS-1ꢀCT
obtained by the exposure show a gradual weight loss of 16.7% up to
200 °C, indicating adsorption of three o-chlorotoluene molecules
per cluster (Fig. S2). During the adsorption, there is no change in
the PXRD pattern (Fig. 3c). Even after the exposure, the crystals still
have enough single crystallinity to perform the single crystal X-ray
analysis. The X-ray crystallographic analysis revealed that the unit
cell parameters and the structure are identical to those of d-POS-1ꢀCT
obtained by recrystallization (Table S2).8 These results indicate
that d-POS-1 has enough chemical stability and pore sustainability
against VOCs. This pore sustainability provides the molecular sieve
effect for VOCs. d-POS-1 selectively adsorbs 1,3,5-trimethylben-
zene (TMB) (Fig. 2) from a mixed solution of TMB and 1,3,5-trieth-
ylbenzene (TEB) or 1,3,5-triisopropylbenzene (TIB). The 1H NMR
spectra after the adsorption at 25 °C display only one singlet peak
at 2.21 ppm, corresponding to methyl groups of TMB (Fig. S3). This
is because TEB and TIB have larger kinetic diameter (9.2 and 9.4 Å,
respectively) than the window of the open channel (9.1 ꢁ 10.4 Å)
in contrast to TMB (8.4 Å). Therefore, d-POS-1 precisely recognizes
molecular size by the rigid open channels to achieve the selective
accommodation. These adsorption behaviors are quite favorable
for convenient and efficient gas and molecular purification.
Figure 3. PXRD patterns of (a) d-POS-1ꢀCT (b) d-POS-1 obtained by guest
desorption under reduced pressure at 150 °C, and (c) d-POS-1ꢀCT after exposure
of d-POS-1 to o-chlorotoluene vapor at 25 °C.
Besides these functionalities as rigid nanoporous architecture,
d-POS-1 also has guest-dependent fluorescence property. As
shown in Figure 5a, d-POS-1ꢀCT and d-POS-1 exhibit blue fluores-
cence with a peak at 420 nm originating in the styryl group in the
host framework. Interestingly, d-POS-1 incorporating N,N-dimeth-
ylaniline (d-POS-1ꢀDMA) affords a remarkable red-shifted fluores-
cence. d-POS-1ꢀDMA is prepared by either recrystallization of the
organic salt 1 from methanol mixed with N,N-dimethylaniline or
exposure of d-POS-1 to N,N-dimethylaniline vapor. TGA data show
20.3% weight loss until 230 °C, indicating incorporation of three
N,N-dimethylanilines per cluster (Fig. S4). The fluorescent spec-
trum of d-POS-1ꢀDMA has a broad profile from 430 to 500 nm to
emit green fluorescence (Fig. 5a). The fluorescent lifetime and
time-resolved emission spectra (TRES) measurements clarify that
the fluorescence in longer wavelength region around 500 nm has
a longer lifetime than that in shorter wavelength region around
430 nm (Table S3, Fig. S5). Nevertheless, the excitation spectrum
of d-POS-1ꢀDMA is quite similar to those of d-POS-1ꢀCT and d-
POS-1, suggesting almost no interactions at the ground state be-
tween the guest molecules and the host framework (Fig. S6). These
results indicate photoinduced charge–transfer (CT) interactions
between the guest molecules and the host framework to provide
red-shifted exciplex fluorescence. N,N-Dimethylaniline and its
derivatives are often utilized as efficient electron donors to form
ground state and photoinduced CT complexes.12 Thus, the guest
molecule acts as an electron donor while the styryl group serves
as an electron acceptor. Of particular note is that the maximum
wavelength of the exciplex fluorescence depends on the ionization
potential of the guest molecules. The fluorescent spectra of d-POS-
1 incorporating N,N-dimethyltoluidine derivatives (Fig. 2) are red-
shifted in proportion to decrease the ionization potential of the
derivatives (DMOT > DMMT > DMPT) (Fig. 5a).12b Exciplex fluores-
cence generally has unique characteristics such as large stokes
shifts and environmental sensitivity.13 Therefore, d-POS-1 is useful
for development not only of solid-state light-emitting devices but
also of chemo-, bio-sensing, and imaging materials.
Figure 4. Gas adsorption isotherms on the d-POS-1 for three adsorbates.
stability of the open channel structure.1c,d The maximum amount
of adsorption of CO2 is 86.5 cm3 gꢂ1 (STP) at P/P0 = 0.99, corre-
sponding to 6.6 CO2 molecules per cluster. An estimated maximum
filling is also calculated from the isotherm to be 88.8 cm3 gꢂ1 (STP).
This adsorption amount is slightly high or comparable with those
of other non-covalent porous materials.1a,g The pore size is calcu-
lated from the Brunauer–Emmett–Teller (BET) method to be
10.9 Å which is almost equal to the crystallographic analysis. BET
surface area is also calculated to be 398 m2 gꢂ1 which is the typical
value for non-covalent porous materials. Meanwhile, there is no
adsorption of N2 and O2 gases at 77 K. This apparent gas selectivity
relates to the kinetic diameters of the gases and the surface char-
acteristic of the void space. The kinetic diameter of CO2 is smaller
than those of N2 and O2 (N2: 3.64 Å, O2: 3.46 Å, and CO2: 3.30 Å).
The static 1D open channels strictly exclude the larger gas mole-
cules. In addition, the channels which are covered with aromatic
In contrast to fluorescent color modulation in response to elec-
tron donor molecules, d-POS-1 also changes its fluorescent inten-
sity by adsorption of electron acceptor molecules such as
nitrobenzene (Fig. 5b). d-POS-1 including nitrobenzene, d-POS-1ꢀNB,
is prepared by either recrystallization of the organic salt 1 from a
groups should enhance CO2 adsorption via p–quadrupole interac-
tions.10 The selective adsorption of CO2 provides potential benefits
to industrial and environmental application such as carbon dioxide
capture and storage (CCS).11

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A. Yamamoto et al. / Tetrahedron Letters 54 (2013) 1268–1273
Figure 5. Guest-dependent fluorescent properties of d-POS-1. (a) Photographs under UV irradiation (k = 365 nm) and normalized fluorescent spectra of d-POS-1 without
guest molecules (GF) and including o-chlorotoluene (CT), N,N-dimethylaniline (DMA), N,N-dimethyl-o-toluidine (DMOT), N,N-dimethyl-m-toluidine (DMMT), and N,N-
dimethyl-p-toluidine (DMPT). (b) Photographs and fluorescent modulation depending on adsorption of nitrobenzene. Inset: Monitoring of fluorescent quantum yield during
guest exchange cycles between nitrobenzene (d-POS-1ꢀNB) and chlorobenzene (d-POS-1ꢀCB). The excitation wavelength was 365 nm.
mixture of methanol and nitrobenzene or exposure of d-POS-1 to
nitrobenzene vapor. The TGA data exhibit 21.7% weight loss until
230 °C, suggesting that d-POS-1ꢀNB incorporates three nitroben-
zene molecules per cluster (Figure S7). As shown in Figure 5b,
the fluorescent intensity rapidly decreased upon exposure to nitro-
benzene to yield exceptionally-low fluorescent quantum efficiency
zeolitic d-POS is the first example for multifunctionalized porosity
combining permanency and guest-responsive photophysical prop-
erty in a non-covalent rigid porous structure. This unprecedented
structure also demonstrates that the strategy based on the clusters
enable to readily and predictably regulate pore size, shape, flexibil-
ity, and affinity with incorporated substances on demand just by
altering sulfonic acid derivatives. The compatibility of the sulfonic
acids also provides convenient tuning of the properties. These
attractive prospects motivate us to apply a wide range of disulfonic
acids such as organic dye and electro- and photo-active molecules.
This study must be a milestone in diverse functional and structural
design of organic porous structures to find a variety of applications.
(UF) (UF <0.01). This fluorescent quenching should also be caused
by strong interactions at the excited state between the styryl group
and nitrobenzene, which often acts as a fluorescence quencher.14
The quenching also occurs by adsorption of other nitro compounds
such as nitrotoluene. These guest-responsive fluorescent decreases
are recovered by removal of nitro compounds by heat treatment or
guest exchange. Nitrobenzene molecules were completely replaced
by chlorobenzene through exposure to chlorobenzene vapor at
25 °C to yield d-POS-1ꢀCB. d-POS-1ꢀCB shows large UF
Acknowledgments
(UF = 0.165) to emit strong blue fluorescence as well as d-POS-
This work was financially supported by the Research fellow-
ships of the Japan Society for the Promotion of Science (JSPS) for
Young Scientists and Grant-in-Aids for Scientific Research on Inno-
vative Areas ‘Coordination Programming’ (area 2107, No.
24108723) from the Ministry of Education, Culture, Sports, Science
and Technology (MEXT), Japan. The synchrotron radiation experi-
ments were performed at BL38B1 in the Spring-8 with the approval
of the Japan Synchrotron Radiation Research Institute (JASRI) (Pro-
posal No. 2007B1988, 2007B2005, 2007B2039 2008A1422, and
2012A1580).
1ꢀCT (Fig. 5b, inset). The switching of the fluorescent intensity is
repeatable without any structural change. These results indicate
that d-POS-1 reversibly switches its fluorescence on and off in
response to the specific guest molecules. Nitro compounds are
generally explosives and explosive-like substances. Thus, easy,
sensitive detection, and separation of nitro compounds have been
important concerning environmental and human safety.14a,c The
combination of selective adsorption and fluorescence modulation
is significantly attractive for development of sensing materials
carrying on detection and separation at once. Furthermore, the
fluorescent modulation in response to electronic structure of the
guest molecules suggests effective interactions between the guest
molecules and the channel surface covered with the fluorophores.
Therefore, d-POS-1 is also expected to act as a light-harvesting
antenna to efficiently utilize light energy for photo reaction and
electrical energy.15
In summary, we demonstrated a sophisticated construction of a
zeolitic diamondoid porous organic salt (d-POS) from a fluorescent
disulfonic acid and triphenylmethylamine. Efficient stability of the
open channel structure provides fully reversible and selective
adsorption behaviors for gas and organic molecules. The d-POS also
shows characteristic fluorescent behaviors whose color and inten-
sity are widely modulated depending on guest molecules. The
Supplementary data
Supplementary data (X-ray crystallographic data and other
physical data of PXRD patterns, TGA, and 1H NMR spectrum, optical
properties for the d-POSs) associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.tetlet.2012.
12.086.
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