Reversible adsorption and separation of aromatics on CdII- triazole single Crystals

Article abstract of DOI:10.1002/chem.200901023

On and off again : Reversible adsorption and separation of a series of aromatic C₆-C₈ compounds (see figure) have been performed on Cd^IIL₂ (L = 4-amino-3,5-bis(4-pyridyl-3-phenyl)1,2,4- triazole) single crystals

Full text of DOI:10.1002/chem.200901023

DOI: 10.1002/chem.200901023
Reversible Adsorption and Separation of Aromatics on CdII–Triazole Single
Crystals
Qi-Kui Liu, Jian-Ping Ma, and Yu-Bin Dong*[a]
The study of coordination-driven self-assembled discrete
and polymeric metal–organic frameworks (MOFs) is a very
active interdisciplinary research area.[1] These metal–organic
assemblies have intriguing structures and potential applica-
tions as smart optoelectronic, magnetic, and catalytic materi-
als. One of the most promising applications for MOFs is
their use as porous materials for molecular adsorption and
separation. Compared with gas storage studies,[2] investiga-
tions into the selective absorption and separation of aromat-
ic molecules on MOFs are rare,[3] especially on MOF single
crystals. For the previous study, efforts were mainly focused
on the phenomenon of single crystal to single crystal trans-
formation (structural dynamism), which is caused by solvent
(coordinated or uncoordinated) exchange, temperature
change, and framework decoration.[4] However, conscious
and systemic studies of guest dynamism, adsorption, and
separation on MOFs that maintain single crystallinity are, to
the best of our knowledge, extremely rare, especially for ar-
omatic molecules, although it is known that the separation
of C6–C8 arenes is very important in industry.[5]
We have been exploring discrete and polymeric porous
MOFs in which bent five-membered heterocycle-bridged li-
gands were chosen as the building blocks. Some of these
MOFs display interesting selective molecular adsorption and
tunable luminescence properties.[6] Herein, we present a pre-
liminary report on a new CdIIL2 (L=4-amino-3,5-bis(4-pyr-
idyl-3-phenyl)-1,2,4-triazole) MOF, formed by simple self-as-
sembly, that functions as a robust host cage for the reversi-
ble encapsulation of benzene and its methyl- and halide-sub-
stituted derivatives. More importantly, it is capable of effec-
tively discerning between these methyl- or halide-
substituted derivatives. Thanks to the unusually stable
nature of the MOF crystals, all absorption and separation
experiments were expediently performed on the single crys-
tals without any deterioration.
The porous CdII MOF used as a selective absorbent was
prepared by treating L (see the Supporting Information)
with [Cd
ACHTNUGTERN(NUGN ClO4)2] in a CH2Cl2/MeOH mixed solvent system
(Scheme 1). Colorless single crystals with a composition of
[CdACTHNURTGENUNG(ClO4)2(L)2]·2CH2Cl2 (1) were isolated in good yield. In
compound 1, ligand L acts as a tridentate ligand to bind CdII
cations into a non-interpenetrating three-dimensional net-
work. The structure crystallizes in the chiral tetragonal
space group P4(3)2(1)2 and the asymmetric unit contains
À
one CdII cation, one L ligand, and two ClO4 ions. Each
ligand binds to three CdII cations by the two terminal pyrid-
À
yl nitrogen atoms and one triazole nitrogen atom (Cd N=
2.328(3)–2.441(3) ꢀ), and each octahedral CdII cation in
turn coordinates to six ligands. The ligands bridge to create
one-dimensional chains of cations connected by terminal
pyridyl moieties. The chains are helical and lie about a 43
axis. These one-dimensional chains are extended along the
crystallographic a and b axes, respectively, and are cross-
linked through the CdII nodes to form a two-dimensional
net (Figure 1). All chains within the net have the same
handedness, which leads to an overall chiral structure. It is
worth noting that there are four sets of this net in 1 that
stack offset along the crystallographic c axis. These nets are
II
À
further linked together by interlayer Cd Ntriazole interac-
tions into a non-interpenetrating three-dimensional porous
framework (Figure 1). The square nanosized channels of 1,
with crystallographic dimensions of about 11ꢁ11 ꢀ, contain
[a] Q.-K. Liu, J.-P. Ma, Prof. Dr. Y.-B. Dong
College of Chemistry, Chemical Engineering and Materials Science
Key Lab of Molecular and Nano Probes, Engineering Research
Center of Pesticideand Medicine Intermediate Clean Production
Ministry of Education
À
disordered CH2Cl2 guest molecules. The ClO4 ions are dis-
persed in the framework (see Figure 2 and the Supporting
Information).
The crystals of 1 can retain their single crystallinity after
the loss of CH2Cl2 guest molecules. Thermogravimetric anal-
ysis (TGA) measurements revealed that the two guest
CH2Cl2 molecules could be removed by heating (1508C,
Shandong Normal University
Jinan, 250014 (P.R. China)
Fax : (+86)531-8261-5258
E-mail: yubindong@sdnu.edu.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200901023.
10364
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Chem. Eur. J. 2009, 15, 10364 – 10368

COMMUNICATION
Scheme 1. The synthesis of [CdACHTUNTRGNEUNG(ClO4)2L2]·2CH2Cl2 (1).
A
(ClO4)2]·o-xylene (5), [Cd(L)2-
2A(ClO4)2]·0.5p-xylene (7;
E
CHTUNGTRENNUNG
see Figure 2). TGA traces indicated that these encapsulated
arenes could be removed at temperatures ranging from 50
to 2708C, and 2 was regenerated when the crystals were
cooled down to room temperature. Therefore, the arene en-
capsulation is reversible. The slightly short distance of 2.9 to
À
3.2 ꢀ between the guest aryl and alkyl C H to the adjacent
phenyl ring on the framework indicates that there are
Figure 1. Left: Single helical l-CdII chain. Center: Two-dimensional net
(middle, two sets of helices are shown in red and blue). Right: Three-di-
mensional non-interpenetrating framework of 1. The four sets of layers
are marked in red, blue, green, and yellow, respectively. The encapsulated
CH2Cl2 molecules have been omitted for clarity.
20 min). Even more astonishing is the fact that the desolvat-
ed crystals retain their single crystallinity up to 3008C, how-
ever, the color of the single crystals changes from colorless
to light brown (see the Supporting Information). When the
crystals were cooled down to room temperature, water mol-
ecules in the air were inevitably encapsulated in the chan-
nels to give a new host–guest system [CdACTHNUGTRNEUNG(ClO4)2(L)2]·H2O
À
(2). The water molecules are hydrogen-bonded to the ClO4
ions in the framework (see the Supporting Information).
Remarkably, compound 2 retains its single crystallinity
even after exchange of different aromatic compounds. If
single crystals of 2 were exposed to benzene, toluene, or o-,
m-, or p-xylene vapor for around one week at room temper-
ature, the X-ray single crystal analysis indicated that the en-
capsulated water molecules had been replaced by the aro-
matic compounds to generate the corresponding host–guest
Figure 2. Reversible absorption of C6–C8 arenes on the single crystals of
2. The encapsulated benzene, toluene, and o-, m-, and p-xylene molecules
are shown as orange, brown, cyan, purple, and yellow, respectively.
systems, that is, [Cd(L)2ACHTUNGTRENUNG(ClO4)2]·2benzene (3), [Cd(L)2-
Chem. Eur. J. 2009, 15, 10364 – 10368
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10365

Y.-B. Dong et al.
À
C H···p interactions between the aromatic guests and the
Additionally, these aromaticꢀCdL2 host–guest systems
show an interesting guest-dependent photoluminescen-
ce.[6b,c,7] Host–guest compounds 3–7 all exhibit blue emission
at around l=470 nm upon excitation at l=320 nm, but with
different intensities. As shown in Figure 4, the emission in-
framework (see the Supporting Information).[7]
Upon further study of this interesting absorption process,
we found that the response time of the cationic CdL2 frame-
work for these aromatic substrates is different. Upon expo-
sure to the corresponding aromatic vapor, fully saturated
samples of 3, 4, 5, 6, and 7 were obtained after 24, 24, 60,
72, and 150 h, respectively, under ambient conditions. Addi-
tionally, compound 2 does not respond to the larger aromat-
ic halides, such as C6H5Cl, C6H5Br, and C6H5I, but is able to
encapsulate C6H5F at 308C (60 h) to give [Cd-
ACHTUNGTRENNUNG
that is, the preparation of a host framework that responds to
a specific substrate in the presence of other different poten-
tial competitors. To explore the molecular selectivity of 2,
an experiment designed to test the binding affinity for ben-
zene, toluene, and o-, m-, and p-xylene was performed.
When the single crystals of 2 were exposed to a mixed
vapor consisting of equivalent molar amounts of benzene,
toluene, and o-, m-, and p-xylene for about one week,
single-crystal structural analysis indicated that only the ben-
zene and toluene guests were selectively absorbed in the
Figure 4. The guest-dependent photoinduced solid-state emission spectra
of 3–7.
tensity increases on going from 3 to 7. This could be attrib-
uted to larger guests that enhance the rigidity of the host
framework and consequently the intraligand p–p* energy.
This tunable luminescent property demonstrates that this
CdII MOF might have applications as a sensor for aromatic
compounds.
channels in
a
1:1 molar ratio to give [Cd-
ACHTUNGTRENNUNG(ClO4)2(L)2]·benzene·toluene (9; see Figure 3 and the Sup-
In summary, a novel chiral porous three-dimensional CdII
MOF has been reported. It can retain single crystallinity
after heating to 3008C. More interesting, it can effectively
recognize and separate methyl- or halide-substituted aro-
matics, which has been expediently confirmed by X-ray
1
single crystal analysis and H NMR spectroscopy. Addition-
ally, the different aromaticꢀCdL2 host–guest systems exhibit
guest-dependent luminescent properties. Work is in progress
to obtain new metal–organic frameworks generated from
other transition metals and bent organic ligands of this type.
Figure 3. Perspective views of 9 and 12. The encapsulated benzene, tolu-
ene, o-, and m-xylene are shown as orange, brown, cyan, and purple, re-
spectively.
Experimental Section
porting Information), which is further confirmed by the
1H NMR spectrum. When crystals of 2 were exposed to a
mixture of benzene and o-, m-, and p-xylene or toluene and
o-, m-, and p-xylene for a week, only benzene or toluene
were encapsulated in the channels to give [Cd-
Synthesis of L: 3,5-Bis(3-iodophenyl)-4-amino-1,2,4-triazole (2.0 mmol),
4-pyridineboronic acid (4.8 mmol), [PdACHTUNRGTNEUNG(PPh3)4] (0.048 mmol), and K2CO3
(6.0 mmol) were added to EtOH/H2O (3:1, 20 mL) and stirred at 75–
808C for 48 h. After removal of the solvent under vacuum, the residue
was purified on silica gel by using column chromatography with CH2Cl2/
THF (2:1) as the eluent to give L as a colorless crystalline solid (yield
74%). 1H NMR (300 MHz, DMSO, 258C, TMS): d=8.71 (d, J=4.9 Hz,
4H; C5H4N), 8.52 (s, 2H; C6H4), 8.30–8.28 (d, J=7.4 Hz, 2H; C6H4),
8.09–8.07 (d, J=7.4 Hz, 2H; C6H4), 7.85 (d, J=4.9 Hz, 4H; C5H4N),
7.80–7.77 (t, J=7.5 Hz, 2H; C6H4), 6.46 ppm (s, 2H; NH2); IR (KBr
pellet): n˜ =3352 (w), 1605 (s), 1486 (ms), 1404 (ms), 1010 (ms), 796 (s),
689 (ms), 622 cmÀ1 (s); elemental analysis calcd (%) for C24H18N6: C
73.83, H 4.65, N 21.52; found: C 73.79, H 4.53, N 21.78.
ACHTUNGTRENNUNG(ClO4)2(L)2]·benzene (10) and [CdCAHTUNGTRENN(UNG ClO4)2(L)2]·toluene (11),
respectively. The same selective absorption experiment was
performed on the single crystals of 2 with o-, m-, and p-
xylene isomers. The single crystal structure analysis and
1H NMR spectra show that almost equivalent amounts of o-
and
m-xylene
were
adsorbed
to
give
[Cd-
Synthesis of 1: A solution of [CdACHTNUGTRENUNG(ClO4)2]·6H2O (5.5 mg, 0.013 mmol) in
MeOH (7 mL) was layered onto a solution of L (5.0 mg, 0.013 mmol) in
CH2Cl2 (7 mL). The solutions were left for about one week at RT, and
ACHTUNGTRENNUNG(ClO4)2(L)2]·0.519o-xylene·0.481m-xylene (12; see Figure 3
and the Supporting Information), whereas no p-xylene was
found in the channels. Thus, compound 2 exhibits similar af-
finity for o- and m-xylene, but no affinity for p-xylene in the
presence of o- and m-xylene competitors.
colorless crystals of [CdACTHNUGTRENNUG(C24H18N6)2AHCUTGNTRNE(NGUN ClO4)2]·2CH2Cl2 were obtained
(yield 78%). 1H NMR (300 MHz, DMSO, 258C, TMS): d=8.70–8.68 (d,
J=5.1 Hz, 4H; C5H4N), 8.45 (s, 2H; C6H4), 8.12–8.10 (d, J=7.6 Hz, 2H;
10366
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Chem. Eur. J. 2009, 15, 10364 – 10368

Reversible Adsorption and Separation of Aromatics
COMMUNICATION
C6H4), 7.98–7.96 (d, J=7.6 Hz, 2H; C6H4), 7.82–7.79 (d, J=5.1 Hz, 4H;
C5H4N), 7.75–7.70 (t, J=7.8 Hz, 2H; C6H4), 6.46 (s, 2H; NH2), 5.75 ppm
(s, 2H; CH2Cl2); IR (KBr pellet): n˜ =3353 (w), 1606 (s), 1486 (s), 1402
(ms), 1091 (s), 1010 (ms), 797 (s), 690 (ms), 622 cmÀ1 (s); elemental anal-
ysis calcd (%) for C50H40CdCl4N12O8: C 47.57, H 3.19, N 13.31; found: C
47.49, H 3.05, N 13.17.
Crystal data for 9: C61H50CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1262.43;
5466.4(9) ꢀ3; Z=4; 1calcd =1.534 gcmÀ3; m
2584; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =25.508; collected/unique
a=15.8471(10),
b=15.8471(10),
c=21.767(3) ꢀ;
V=
A
ACHTUNGTRENNUNG(000)=
AHCTUNGTRENNUNG
reflections: 28805/5086 [Rint =0.0503]; R1 (I>2s(I))=0.0395; wR2 (I>
2s(I))=0.0990.
Crystal data for 10: C54H42CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
Synthesis of 2: Single crystals of 1 were heated in air at 1508C for 20 min
1170.30;
5420.7(8) ꢀ3; Z=4; 1calcd =1.434 gcmÀ3; m
2384; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =25.508; collected/unique
a=15.8506(10),
b=15.8506(10),
c=21.576(3) ꢀ;
V=
and then cooled down to RT. The X-ray single crystal analysis and
1H NMR spectrum indicated that [Cd
ed.
ACHTNUGTNERN(NUG ClO4)2(L)2]·H2O (2) was generat-
A
ACHTUNGTRENNUNG(000)=
AHCTUNGTRENNUNG
reflections: 25996/4959 [Rint =0.0778]; R1 (I>2s(I))=0.0509; wR2 (I>
2s(I))=0.1320.
Synthesis of 3–12: Single crystals of 2 were placed in a small open vial
and then sealed in a larger vial that contained the corresponding aromat-
ic solvent or mixed aromatic solvents. X-ray single crystal analysis and
1H NMR spectroscopy were directly performed on these adsorption-satu-
rated crystals. The characterization data are consistent with the resulting
structures.
Crystal data for 11: C55H44CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1184.32;
5466.5(8) ꢀ3; Z=4; 1calcd =1.439 gcmÀ3; m
2416; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =25.508; collected/unique
a=15.9030(12),
b=15.9030(12),
c=21.615(2) ꢀ;
V=
A
ACHTUNGTRENNUNG(000)=
AHCTUNGTRENNUNG
reflections: 28822/5090 [Rint =0.0491]; R1 (I>2s(I))=0.0387; wR2 (I>
2s(I))=0.0938.
Crystallographic data
Crystal data for 1: C50H40CdCl6N12O8; tetragonal; P4(3)2(1)2; Mr =
1262.04; a=15.869(3), b=15.869(3), c=21.649(5) ꢀ; V=5451.8(19) ꢀ3;
Crystal data for 12: C56H46CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1198.35;
5411.2(9) ꢀ3; Z=4; 1calcd =1.471 gcmÀ3; m
2456; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =25.508; collected/unique
a=15.9030(11),
b=15.9030(11),
c=21.396(3) ꢀ;
V=
Z=4; 1calcd =1.538 gcmÀ3
123(2) K;
(MoKa)=0.759 mmÀ1
; mACHTUNGTRENNUGN ; FACHTNUGTRENNNUG
A
ACHTUNGTRENNUNG(000)=
lACHTUNGTRENNUNG
AHCTUNGTRENNUNG
tions: 28514/5076 [Rint =0.0605], R1 (I>2s(I))=0.0556, wR2 (I>2s(I))=
0.1539.
reflections: 28949/5346 [Rint =0.0455]; R1 (I>2s(I))=0.0549; wR2 (I>
2s(I))=0.1354.
Crystal data for 2: C48H38CdCl2N12O9; tetragonal; P4(3)2(1)2; Mr =
1110.20; a=15.916(3), b=15.916(3), c=21.495(7) ꢀ; V=5445(2) ꢀ3; Z=
CCDC-721802 (1), -721803 (2), -721804 (2’, 1508C), -721805 (2’’, 3008C),
-721806 (3), -721807 (4), -721808 (5), -721809 (6), -721810 (7), -721811
(8), -721812 (9), -721813 (10), -721814 (11), and -721815 (12) contain the
supplementary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
4; 1calcd =1.354 gcmÀ3
123(2) K;
;
m
G
;
FACHTUNGTRENNUNG
lACHTUNGTRENNUNG
tions: 27744/5069 [Rint =0.0993], R1 (I>2s(I))=0.0566, wR2 (I>2s(I))=
0.1601.
Crystal data for 3: C60H48CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1248.40;
5455.1(13) ꢀ3; Z=4; 1calcd =1.520 gcmÀ3; m
2552; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =26.08; collected/unique
reflections: 29914/5380 [Rint =0.0665]; R1 (I>2s(I))=0.0408; wR2 (I>
2s(I))=0.0933.
a=15.8267(16),
b=15.8267(16),
c=21.778(4) ꢀ;
V=
ACHTUNGTRNE(NUNG 000)=
A
ACHTUNGTRENNUNG
Acknowledgements
We are grateful for financial support from the National Natural Science
Foundation of China (grant nos. 20871076 and 20671060), the Shangdong
Natural Science Foundation (grant no. JQ200803), and the Ph.D. Pro-
grams Foundation of the Ministry of Education of China (grant no.
200804450001).
Crystal data for 4: C62H52CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1276.46;
5450.2(10) ꢀ3; Z=4; 1calcd =1.556 gcmÀ3; m
2616; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =25.508; collected/unique
a=15.8698(12),
b=15.8698(12),
c=21.641(3) ꢀ;
V=
A
ACHTUNGTRNE(NUNG 000)=
ACHTUNGTRENNUNG
reflections: 28252/5076 [Rint =0.0720]; R1 (I>2s(I))=0.0455; wR2 (I>
2s(I))=0.1062.
Keywords: adsorption
luminescence · metal–organic frameworks
· arenes · chiral frameworks ·
Crystal data for 5: C56H46CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1198.35; a=15.884(3), b=15.884(3), c=21.440(7) ꢀ; V=5409(2) ꢀ3; Z=
4; 1calcd =1.472 gcmÀ3
123(2) K;
;
m
(MoKa)=0.570 mmÀ1
;
FACHTUNGTRENNUNG
lACHTUNGTRENNUNG
tions: 27046/5031 [Rint =0.0925]; R1 (I>2s(I))=0.0534; wR2 (I>2s(I))=
0.1228.
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Crystal data for 6: C56H46CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1198.35; a=15.905(2), b=15.905(2), c=21.548(5) ꢀ; V=5451.3(17) ꢀ3;
Z=4; 1calcd =1.460 gcmÀ3
123(2) K;
(MoKa)=0.565 mmÀ1
; mACHTUNGTRENNUGN ; FACHTNUGTRENNNUG
lACHTUNGTRENNUNG
˘
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Crystal data for 7: C52H41CdCl2N12O8; tetragonal; P4(3)2(1)2; Mr =
1145.27;
5413.3(10) ꢀ3; Z=4; 1calcd =1.405 gcmÀ3; m
2332; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =25.508; collected/unique
a=15.8774(12),
b=15.8774(12),
c=21.474(3) ꢀ;
V=
A
ACHTUNGTRNE(NUNG 000)=
ACHTUNGTRENNUNG
reflections: 28092/5046 [Rint =0.0707]; R1 (I>2s(I))=0.0493; wR2 (I>
2s(I))=0.1202.
Crystal data for 8: C54H41CdCl2FN12O8; tetragonal; P4(3)2(1)2; Mr =
1188.29;
5424.9(9) ꢀ3; Z=4; 1calcd =1.455 gcmÀ3; m
2416; T=123(2) K; l(MoKa)=0.71073 ꢀ; qmax =25.498; collected/unique
a=15.8475(10),
b=15.8475(10),
c=21.601(3) ꢀ;
V=
A
ACHTUNGTRNE(NUNG 000)=
ACHTUNGTRENNUNG
reflections: 26792/5043 [Rint =0.0574]; R1 (I>2s(I))=0.0435; wR2 (I>
2s(I))=0.1151.
Chem. Eur. J. 2009, 15, 10364 – 10368
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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