A Family of Metal-Organic Frameworks with a New Chair-Conformation Resorcin[4]arene-Based Ligand: Selective Luminescent Sensing of Amine and Aldehyde Vapors, and Solvent-Mediated Structural Transformations

Article abstract of DOI:10.1021/acs.cgd.6b00213

By utilizing a new chair-conformation resorcin[4]arene-based octacarboxylate ligand, four functional metal-organic frameworks (MOFs), namely, [(CH₃)₂NH₂]₄[Cd₂(L)]·4H₂O (1), [(CH₃

Full text of DOI:10.1021/acs.cgd.6b00213

Article
pubs.acs.org/crystal
A Family of Metal−Organic Frameworks with a New Chair-
Conformation Resorcin[4]arene-Based Ligand: Selective Luminescent
Sensing of Amine and Aldehyde Vapors, and Solvent-Mediated
Structural Transformations
†
,†
†
,‡
,†
Hang Zhang, Jin Yang,* Ying-Ying Liu, Shuyan Song,* and Jian-Fang Ma*
†Key Laboratory of Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, P. R.
China
‡
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun 130022, P. R. China
*
S Supporting Information
ABSTRACT: By utilizing a new chair-conformation
resorcin[4]arene-based octacarboxylate ligand, four functional
metal−organic frameworks (MOFs), namely, [(CH ) NH ] -
3
2
2 4
[
(
[
Cd (L)]·4H O (1), [(CH ) NH ] [Zn (L)]·2DMF·6H O
2 2 3 2 2 4 2 2
2), [(CH ) NH ] [Co (L)]·2DMF·4H O (3), and
3
2
2
4
2
2
(CH ) NH ] [Co (L)(H O) ] (4) (H L = 2,8,14,20-tetra-
3 2 2 2 3 2 12 8
methylphenyl-4,6,10,12,16,18,22,24-octa-carboxymethoxy-
resorcin[4]arene and DMF = N,N-dimethylformamide), were
solvothermally synthesized and structurally characterized. In 1,
each L8 anion bridges eight Cd(II) atoms to give a three-
−
6
12 10
6
8−
dimensional (3D) (4,8)-connected (4 )(4 .6 .8 ) framework. In isostructural 2 and 3, each L anion links eight adjacent
6
11 12
5
8−
Zn(II) or Co(II) atoms to yield a 3D (4,8)-connected (4 )(4 .6 .8 ) net. In 4, each L anion only bridges four Co(II) atoms
by using its four carboxylates each in a monodentate coordination mode to generate an infinite one-dimensional (1D) chain.
Remarkably, the highly selective luminescent sensing of amine and aldehyde vapors was studied for 1 and 2 as fluorescent
sensors. Importantly, a solvent-induced structural transformation from the 1D chain to the 3D porous framework between 3 and
4
was also investigated in detail.
3
0,31
INTRODUCTION
safety.
Therefore, fluorescent detecting of these volatile
32
■
species has also become a significant topic. However, only a few
examples of fluorescent MOFs involving aldehyde or amine
sensing in the vapor phase have been reported thus far.
On the other hand, engineered MOFs involving trans-
formations of their structures and properties by external stimuli,
such as solvent, heat, guest removal, oxidation of metal centers,
Metal−organic frameworks (MOFs) have attracted a great deal
of attention owing to their potential applications in catalysis, gas
storage, chemical sensing, magnetic properties, etc.
regard, luminescent MOFs as fluorescent sensors have received
33
1
−15
In this
intense interest for their huge superiority in unique photo-
16−18
physical properties.
The MOFs with variable structures and
3
4−40
1
9−21
and light,
have received considerable current interest.
tunable fluorescence give them good selectivity.
the molecular level interactions between the framework and the
Moreover,
Among various factors mentioned above, the effects of the
solvents on the structural transformations which involve changes
in structural dimensionality resulting from cleavage and
regeneration of coordination bonds are particularly attrac-
analytes could reduce detection limits, thereby showing high
2
2−24
sensitivity.
Over the past several years, fluorescent MOFs
have achieved great success in the trace detection of small organic
molecules in liquid form.
4
1,42
2
5,26
tive.
Usually, organic ligands have a very important role in the
Since the first report of the highly
luminescent [Zn (bpdc) (bpee)] (bpdc = 4,4′-biphenyldicar-
2
2
43,44
design and synthesis of functional MOFs.
modified calixarenes with a large number of substituents became
a new series of very versatile organic ligands.
resorcin[4]arenes, their body and/or rims could be modified,
In this context, the
boxylate and bpee = 1,2-bipyridylethene) capable of detecting
nitroaromatics in the vapor phase, studies employing the MOFs
as luminescent sensors for vapor phase detections have been
45−50
In the case of
27
intensively pursued. Very recently, a new two-dimensional
2D) mapping strategy has been developed for the effective
which greatly enriched the structural diversities of the functional
(
detection of vaper analysts by using changes in fluorescence
intensity and emission wavelength of the fluorescent MOF
Received: February 9, 2016
Revised: March 28, 2016
2
8,29
sensors.
Typical harmful vapors such as volatile aldehydes
and amines are of great concern for the environment and food
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Scheme 1. Synthesis of Resorcin[4]arene-Functionalized Octacarboxylic Acid H8L
5
1,52
MOFs.
Several years ago, our group initiated a continuous
Synthesis of l,3-Bis[(methoxycarbonyl)methoxy]benzene
(
1
L1). MeCN (300 mL) was added to a mixture of resorcinol (11.10 g,
investigation into the coordination chemistry of modified
resorcin[4]arenes, and several series of resorcin[4]arenes-based
MOFs, featuring fascinating motifs and properties, were
00 mmol), anhydrous K CO3 (34.5 g, 250 mmol), methyl
2
chloroacetate (27.1 g, 250 mmol), and KI (0.5 g, 3 mmol). After
heating at reflux for 48 h under nitrogen gas, the solvent was removed. A
total of 200 mL of water was added to the residue, and the mixture was
extracted by chloroform (3 × 200 mL). The organic phase was dried
with anhydrous Na SO . After the chloroform was removed, the residue
5
1,53−58
reported.
Nevertheless, there is not a reported example
that chair-conformation functionalized resorcin[4]arenes as
organic linkers were employed for constructing functional
MOFs.
On the basis of the above consideration, we synthesized a new
resorcin[4]arene-functionalized octacarboxylate ligand,
,8,14,20-tetra-methylphenyl-4,6,10,12,16,18,22,24-octa-carbox-
ymethoxy-resorcin[4]arene (H L) (Scheme 1), in which two
benzyl groups are at the upper edge of the resorcin[4]arene
skeleton, and the remaining two are at the lower one, showing a
chair conformation. By using the chair-conformation
2
4
was recrystallized in methanol to afford L1 in a yield of 55%. Anal. Calcd
for C H O (M = 254.24): C, 56.69; H, 5.55. Found: C, 56.82; H,
12
14
6
r
5.41.
Synthesis of H L. A mixture of L1 (2.56 g, 10.0 mmol) and p-
8
tolualdehyde (1.20 g, 10 mmol) in dichloromethane (30 mL) was stirred
2
8
in an ice bath for 0.5 h with dropwise addition of BF ·OEt (6 mL). Then
3
2
the mixture was stirred at room temperature overnight. The solid was
collected and washed by using CH Cl to give L2 in a yield of 78%. Then
2
2
sodium hydroxide (1.6 g, 40 mmol), tetrahydrofuran (150 mL), and
water (150 mL) were added into the obtained L2. After heating at reflux
for 8 h, the solvents were removed, and then 100 mL of water was added.
resorcin[4]arene-based octacarboxylate H L, four new MOFs,
8
namely, [(CH ) NH ] [Cd (L)]·4H O (1), [(CH ) NH ] -
3
2
2 4
2
2
3 2
2 4
[
Zn (L)]·2DMF·6H O (2), [(CH ) NH ] [Co (L)]·2DMF·
−1
2
2
3 2
2 4
2
pH value was adjusted to 1−2 by using HCl (1.0 mol·L ), and then the
4
H O (3), and [(CH ) NH ] [Co (L)(H O) ] (4) (DMF =
obtained solid was collected, washed with water, and dried in air to give
2
3 2
2 2
3
2
12
N,N-dimethylformamide), have been synthesized and structur-
ally characterized. Remarkably, the highly selective and sensitive
luminescent probing of benzaldehyde and aniline vapors was
explored for 1 and 2 as fluorescent sensors. More importantly,
the solvent-induced structural transformation from the one-
dimensional (1D) chain to the three-dimensional (3D) porous
framework between 3 and 4 was also studied.
H L in a yield of 60%. Anal. Calcd for C H O (M = 1313.26): C,
65.85; H, 4.91. Found: C, 66.02; H, 4.65.
8
72 64 24
r
Synthesis of [(CH ) NH ] [Cd (L)]·4H O (1). H L (0.027 g, 0.025
3 2
2 4
2
2
8
mmol) and Cd(Ac) ·2H O (0.012 g, 0.05 mmol) were dissolved in a
2
2
mixture of DMF (6 mL) and H O (2 mL). Then the mixture was sealed
2
in a Teflon reactor (15 mL) and heated at 110 °C for 3 days. Crystals of 1
were isolated in a 25% yield based on Cd(II) after cooling the Teflon
reactor to room temperature. Anal. Calcd for C H O N Cd (M =
80
96 28
4
2
r
1
786.45): C, 53.70; H, 5.58; N, 3.01. Found: C, 53.82; H, 5.45; N, 3.14.
−1
EXPERIMENTAL SECTION
IR data (KBr, cm ): 3421(w), 3048 (m), 3020(m), 2922(m), 2861(m),
■
2
1
801(m), 2480(s), 1585(w), 1498(w), 1410(w), 1284(w), 1187(w),
157(m), 1101(w), 1060(w), 1023(m), 926(s), 895(s), 857(s), 810(s),
Materials and Measurements. All chemical reagents were
achieved from commercial sources. Powder X-ray diffraction (PXRD)
patterns were determined on a Rigaku Dmax 2000 X-ray diffractometer.
The FT-IR spectra were collected on a Mattson Alpha Centauri
spectrometer. The UV−vis spectra were measured on a Cary 500
spectrophotometer. Elemental analysis data (C, H, and N) were
collected on a PerkinElmer 240 elemental analyzer. The emission
spectra are measured on a FLSP920 Edinburgh fluorescence
spectrometer. Magnetic susceptibility data are collected on a SQUID
magnetometer (Quantum Design, MPMS-5) with an applied field of
720(s), 600(s), 698(s).
Synthesis of [(CH
L (0.027 g, 0.025 mmol), Zn(Ac)
(4 mL), and H O (4 mL) was sealed in a Teflon reactor (15 mL) and
) NH
2
] [Zn
4
(L)]·2DMF·6H
O (2). A mixture of
2
·2H O (0.012 g, 0.05 mmol), DMF
3
2
2
H
8
2
2
2
heated at 120 °C for 3 days. Crystals of 2 were isolated in a 30% yield
based on Zn(II) after cooling the Teflon reactor to room temperature.
Anal. Calcd for C86H N O32Zn (M = 1866.60): C, 55.39; H, 5.72; N,
106 6 2 r
4.56. Found: C, 55.26; H, 5.85; N, 4.44. IR data (KBr, cm ): 3440(m),
3254(m), 3154(m), 3050(m), 3021(w), 2913(m), 2857(m), 2784(m),
2523(s), 2427(s), 1667(w), 1626(w), 1586(w), 1500(w), 1471(m),
−1
1000 Oe. Thermogravimetric data were determined on a PerkinElmer
TG-7 analyzer.
B
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Table 1. Crystal Data and Structure Refinements for 1−4
1
2
3
4
formula
Mr
C H O N Cd
C H N O Zn
C H Co N O
C H Co O N
76 86 3 36 2
8
0
96 28
4
2
86 106
6
32
2
86 106
2
6
30
1786.45
C2/c
1866.60
1821.65
1780.28
space group
a/Å
P2 /n
1
P2 /n
1
P1
̅
29.0460(9)
21.4360(6)
14.6820(5)
90
11.8040(5)
24.8100(9)
15.6720(7)
90
11.8380(8)
24.7720(15)
15.7730(8)
90
11.4780(8)
12.2130(9)
18.3460(13)
74.655(6)
82.714(6)
86.954(6)
2459.5(3)
1
b/Å
c/Å
α/°
β/°
γ/°
V/Å3
93.618(3)
90
96.269(4)
90
96.834(5)
90
9123.2(5)
8
4562.2(3)
4
4592.6(5)
4
Z
3
D (g/cm )
1.301
1.359
1.317
1.202
c
GOF on F2
0.999
1.019
1.015
1.175
a
R1 [I > 2σ(I)]
0.0555
0.1652
0.0598
0.1625
0.0436
0.0818
0.2269
0.0896
0.1193
b
wR2 (all data)
0.2863
Rint
0.0312
0.0620
a
R = Σ||F | − |F ||/Σ|F |. wR = {Σ[w(F − F ) ]/Σw(F ) ]}1/2.
b
2
2
2
2 2
1
o
c
o
2
o
c
o
Figure 1. (a) View of the coordination environment of Cd(II) atom in 1. (b) View of the coordination mode of L anion. Symmetry codes: #1 −x− 1/2,
8
−
#
2
#3
#4
−
y+ 1/2, −z + 1; −x, y, −z + 1/2; −x − 1/2, −y + 1/2, −z; x, −y + 1, z+ 1/2. (c) View of the 3D framework of 1. (d) Schematic representation of
the 3D (4,8)-connected net of 1.
−1
1
1
6
420(w), 1342(s), 1314(w), 1280(w), 1257(w), 1189(w), 1156(m),
100(w), 1062(w), 1025(m), 929(s), 899(s), 857(s), 809(s), 694(m),
64(s), 614(s), 594(s), 550(s), 509(s), 450(s), 412(s).
C, 56.78; H, 5.75; N, 4.72. IR data (KBr, cm ): 3401(m), 3048(m),
3020(m), 2924(w), 2860(m), 2485(s), 1716(m), 1651(w), 1609(w),
1584(w), 1497(w), 1286(w), 1187(w), 1156(m), 1102(m), 1062(w),
1024(m), 927(s), 896(s), 853(s), 812(s), 729(m), 693(m), 600(s),
502(s).
Synthesis of [(CH ) NH ] [Co (L)]·2DMF·4H O (3). The synthesis
3
2
2 4
2
2
of 3 is analogous to that of 1 except that Co(Ac) ·4H O (0.014 g, 0.05
2
2
mmol) was utilized instead of Cd(Ac) ·2H O. Purple crystals of 3 were
isolated in a 28% yield based on Co(II). Anal. Calcd for
Synthesis of [(CH ) NH ] [Co (L)(H O) ] (4). The synthesis of 4
2
2
3 2
2 2
3
2
12
is analogous to that of 3 except that the ratio of DMF (4 mL) and H O
2
C H Co N O (M = 1821.65): C, 56.64; H, 5.56; N, 4.97. Found:
(4 mL) was changed to 1:1. The pink crystals were achieved in a 18%
86
106
2
6
30
r
C
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
#
1
#2
Figure 2. (a) Diagram showing the coordination environment of Zn(II) atom in 2. Symmetry codes: −x− 1/2, y − 1/2, −z+ 3/2; −x+ 1/2, y − 1/2,
#3
#4
8−
−
z + 3/2; −x, −y+ 1, −z + 2; −x, −y + 1, −z + 1. (b) View of the coordination mode of L anion. (c) View of the 3D framework of 2. (d) Schematic
6 11 12 5
representation of the (4,8)-connected (4 )(4 .6 .8 ) net of 2.
yield based on Co(II). Anal. Calcd for C H Co O N (M =
Crystal Structure Determinations. The intensity data of 1−4
were measured on a Oxford Diffraction Gemini R Ultra diffractometer
with graphite-monochromated Mo−Kα radiation (λ = 0.71073 Å).
Starting structural models were solved by direct method of SHELXS-97
76
86
3
36
2
r
1
780.28): C, 51.17; H, 4.91; N, 1.78. Found: C, 51.36; H, 4.79; N, 1.67.
−1
IR data (KBr, cm ): 3631(m), 3452(w), 3048(m), 3019(m) 2927(m),
2
1
8
6
365(s), 2339(s), 1642(w), 1584(w), 1495 (w), 1427(w), 1329(m),
290(m), 1232(m), 1188(w), 1155(w), 1096(w), 1058(w), 925(s),
74(s), 841(s), 811(m), 791(s), 772(s),739(m), 689(m), 642(s),
02(s), 550(s), 506(m).
2
and refined by full-matrix least-squares techniques on F using the
5
9−61
SHELXL-97 program within WINGX.
Non-hydrogen atoms were
refined anisotropically. Hydrogen atoms of the water molecules were
not located from the difference Fourier maps. During the refinements of
1 and 4, the SQUEEZE functions in PLATON were applied to remove
Measurement for Luminescent Sensing of Volatile Aldehyde
and Amine Vapors. The as-synthesized samples of 1 and 2 were
immersed into anhydrous methanol for 3 days, and then the methanol
solvent was refreshed three times during the exchange. After the removal
of methanol by centrifuging, the wet sample was dried under a vacuum at
62
the contribution of reflection by disordered solvent molecules. Further
crystallographic details are listed in Table 1. Selected bond distances and
angles are given in Tables S1−S4.
80 °C for 10 h to give the activated samples of 1 and 2. Then, a small
beaker (10 mL) with the activated samples (10 mg) was placed into a big
sealed container (50 mL) with given solvent (20 mL) for 24 h (Figure
S1). Subsequently, the small beaker was taken out from the container
and quickly sealed, and the emission spectra were measured by using the
solid samples. The initial emission spectrum of the solid sample was
measured in a solid sample holder before exposure to various solvent
vapors.
To test the response rate of 1 and 2 toward the benzaldehyde and
aniline vapors, the time-dependent fluorescence quenching profile was
measured. The activated samples of 2 (50 mg) were ground into
powder, and then were further pressed into firm sheet samples. The firm
sheet was stuck on a quartz slide through a double-side adhesive. The
cuvette containing the sensor slide was adjusted to a suitable position
RESULTS AND DISCUSSION
■
Structure of [(CH ) NH ] [Cd (L)]·4H O (1). The asym-
3 2
2 4
2
2
metric unit of 1 consists of one Cd(II) cation, one-half-occupied
8−
+
L
anion, two [H N(CH ) ] cations, and two lattice water
2 3 2
molecules, as illustrated in Figure 1a. Each Cd(II) atom is
surrounded by five carboxylate oxygen atoms from four different
8−
#1
L
anions (Cd1−O2 = 2.234(5), Cd1−O4 = 2.190(4), Cd1−
#2
#3
#3
O8 = 2.352(3), Cd1−O9 = 2.449(3), Cd1−O10 = 2.261(3)
Å) in a distorted trigonal bipyramid geometry. Remarkably, each
8−
L
anion exhibits a chair conformation and links eight Cd(II)
cations by using its eight carboxylates (Figure 1b). In this
manner, adjacent Cd(II) atoms are interconnected by L anions
to give an extended 3D framework, as illustrated in Figure 1c. It is
8−
(Figure S2). The solid state emission spectra of the firm sheet samples
were determined as an original standard. Then, benzaldehyde or aniline
solution (100 μL) was added into the cuvette by toppette pipettor. The
cuvette was then sealed carefully by the cap. The emission spectra as well
as the responses of the sensor slide versus time plots were measured in
benzaldehyde or aniline vapors.
noteworthy that the negative charges of the framework are
+
balanced by (CH ) NH2 cations, which results from the
3 2
decomposed DMF solvents (Figure S3a). After removal of the
solvent molecules, the free volume calculated by PLATON
D
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 3. (a) Diagram showing the coordination environments of Co(II) atoms in 4. Symmetry codes: −x + 1, −y, −z− 1; #2 −x, −y, −z. (b)
#1
Coordination mode of the L8 anion. (c) View of the 1D chain in 4. (d) View of the 3D supramolecular architecture of 4.
−
Figure 4. A diagram showing the parameters of solvent ratio and
reaction temperature. Unknown phase (green triangles), powder phase
of 3 (yellow circle), pure crystalline phase of 3 (blue square), pure
crystalline phase of 4 (pink circle).
Figure 5. Photographs and PXRD patterns of as-synthesized 4 and after
being handled by DMF.
6
2
#3
#1
#2
analysis is ca. 38.1%. Topologically, if both Cd(II) atom and
L
Zn1−O3 = 1.967(2), Zn1−O8 = 1.925(2), Zn1−O10
=
8
−
8−
anion can be classified as 4- and 8-connected nodes,
respectively, the overall 3D framework of 1 can be described as a
4,8)-connected (4 )(4 .6 .8 ) net (Figure 1d).
1.939(2) Å). Each carboxylate of the L anion displays a
monodentate coordination mode (Figure 2b). In this manner,
each L anion bridges adjacent eight Zn(II) cations to yield a 3D
6
12 10
6
8−
(
Structures of [(CH ) NH ] [Zn (L)]·2DMF·6H O (2) and
framework (Figure 2c). Topologically, if both Zn(II) atom and
3
2
2 4
2
2
8−
[
(CH ) NH ] [Co (L)]·2DMF·4H O (3). Compounds 2 and 3
L
anion are considered as 4- and 8-nodes, respectively, the
3
2
2 4
2
2
are isostructural (Figure S4) and crystallize in the same
overall structure of 2 can be simplified as a (4,8)-connected
6
11 12 5
monoclinic space group P2 /n. Hence, only the structure of 2
(4 )(4 .6 .8 ) net (Figure 2d). For 2 and 3, the solvent-
1
is described here. As illustrated in Figure 2a, the asymmetric unit
accessible volumes calculated by PLATON analysis are 36.8%
and 36.3%, respectively, after removal of the solvent molecules.
Moreover, the void dimensions for 1 and 2 are ca. 4.0 and ca. 5.4
Å, respectively, as shown in Figure S5.
8−
62
of 2 is composed of one Zn(II) cation, one-half-occupied L
+
anion, two [H N(CH ) ] cations, three lattice water molecules,
2
3 2
and one lattice DMF molecule. Each Zn(II) atom is in a distorted
tetrahedral sphere, coordinated by four carboxylate oxygen
Structure of [(CH ) NH ] [Co (L)(H O) ] (4). As depicted
3
2
2 2
3
2
12
8
−
atoms from four different L anions (Zn1−O1 = 1.942(2),
in Figure 3a, the asymmetric unit of 4 contains one and a half
E
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 6. (a) Changes of coordination environments of Co(II) atoms and coordination modes of L8− anions. The yellow ball and red ball represent
water oxygen atom and carboxylate oxygen atom, respectively. (b) View of the solvent-induced structural transformation from 4 to 3.
, each L8 anion in 4 only bridges four Co(II) atoms by using its
−
3
four carboxylates each in a monodentate coordination mode
Figure 3b). In this fashion, Co1 and its symmetry-related
(
8
−
species are bridged by L anions to give an infinite 1D chain, as
depicted in Figure 3c. Co2 and its symmetry-related ones are
located on both sides of the chain. Noticeably, the short O···O
contacts between water molecules and L8 anions (O1W···O1 =
−
2
.615 Å, O2W···O10 = 2.727 Å and O4W···O10 = 2.584 Å)
suggest the existence of O−H···O hydrogen bonds, although the
hydrogen atoms of the O1W, O2W, and O4W were not located
from the difference Fourier maps. Further, adjacent 1D chains
are linked by the O···O contacts into a 3D supramolecular
architecture (Figure 3d).
Solvent-Induced Structural Transformation between 3
and 4. During the syntheses of Co(II)-based compounds 3 and
4
, we found that the solvent ratio and reaction temperature have
Figure 7. Emission spectra of H L, 1, and 2 in solid state at room
8
crucial roles in the formation of their resulting frameworks. As a
result, numerous parallel experiments were performed by varying
the solvent ratios as well as the reaction temperatures. To give an
overview of synthetic conditions of 3 and 4, a diagram showing
the parameters of solvent ratios and reaction temperatures is
temperature.
8
−
Co(II) cations, one-half-occupied L anion, and one [H N-
2
+
(
CH ) ] cation (Figure S3b). Notably, two Co(II) cations show
3 2
different coordination modes. Co1, lying at an inversion center, is
coordinated by two carboxylate oxygen atoms of two different
provided in Figure 4. When the solvent ratios (DMF/H O) are
2
8
−
#1
1:7 and 1:3, no crystals of 3 and 4 are produced at all temperature
ranges. By increasing the solvent ratio to 3:5 or 1:1, crystals of 3
could be obtained at 110 or 120 °C. When the solvent ratio
reaches 5:3, a powder phase of 3 appears at 120 °C, which was
confirmed by PXRD patterns (Figure S6). By further increasing
the solvent ratio to 3:1 or 7:1, only crystals of 3 were formed at
120 °C or above temperature. The above results demonstrate
that crystals of 3 can be easily produced from the components
with a high solvent ratio between DMF and water at relatively
L
anions (Co1−O1 = 2.077(4), Co1−O1 = 2.078(4) Å) and
four water oxygen atoms (Co1−O1W = 2.095(4), Co1−O2W =
#1
#1
2
.101(4), Co1−O1W = 2.095(4), Co1−O2W = 2.101(4) Å)
in an octahedral environment. Co2 is coordinated by one
8−
carboxylate oxygen atom from one L anion (Co2−O3 =
2
2
.136(5) Å) and four water oxygen atoms (Co2−O3W =
.068(13), Co2−O4W= 1.967(13), Co2−O6W = 2.046(15),
Co2−O5W = 2.066(17) Å) in a distorted pyramidal
coordination geometry (Figure 3a). Different from those in 1−
F
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 8. Luminescent intensities of 1 (a) and 2 (b) in the temperature range of 80−280 K.
high temperatures. When the solvent ratio (DMF/H O) and the
reaction temperature were reduced, crystals of 4 were formed.
water, the Co−O (water) bonds are gradually broken in 4, and
the new Co(II)−O (carboxylate) bonds are formed in 3, leading
to the 1D chain into the 3D framework (Figure 6b).
2
3
and 4 is assembled from the identical materials under similar
1
0
conditions, which encouraged us to explore their possible
structural conversion further. Fortunately, upon handling the as-
synthesized 4 in DMF at 120 °C for 48 h, 4 undergoes a solvent-
induced structural transformation to form 3. As shown in Figure
Luminescent Properties. MOFs containing d metals have
attracted considerable attention because of their promising
64−66
application as luminescent sensor materials.
The solid state
emission spectra of free H L ligand, 1, and 2 are measured at
8
5, the crystal colors changed from pale pink to purple. Both single
room temperature, as shown in Figure 7. Upon excitation at 323
crystal X-ray diffraction and PXRD patterns confirm that crystals
of 4 have completely transformed into 3. This transformation is
proposed to probably be a solvent-induced structural trans-
formation, which may involve the dissolution of 4 and
recrystallization of 3 in DMF. Very recently, a striking single-
crystal-to-single-crystal (SCSC) transformation associated with
the dissolution and recrystallization process from the achiral
nm, the free H L ligand displays an emission peak at 490 nm,
8
which probably accounts for the π* → π or π* → n
67,68
transitions.
Compounds 1 and 2 show emissions at 514
(λ = 324 nm) and 493 nm (λ = 324 nm), respectively, which
ex
ex
are mainly based on the H L ligand because of their similar
8
69,70
emission peaks.
To explore the effect of measurement temperature on the
[
Ni(NO -ip)(bimb)(μ-H O)] ·(H O) to chiral [Ni (NO -
luminescent intensities, the emission spectra of 1 and 2 were
2 2 n 2 n 4 2
ip) (bimb) (OH) (H O)] ·(CH CH OH) (NO -H ip = 5-
nitroisophthalic acid and bimb = 1,4-bis(imidazol-1′-yl)butane)
has been observed. It should be mentioned that no single
crystals of 3 were achieved when raw materials were treated in
DMF at 120 °C. Thus, this solvent-induced structural trans-
formation provides an alternative method for the crystal
synthesis of 3.
The solvent-induced structural transformation from 4 to 3 is
involved in the cleavage and regeneration of Co−O bonds. As
shown in Figure 6a, each Co(II) atom in 4 is surrounded by six
oxygen atoms from four water molecules and two carboxylates,
while the Co1 center in 3 is only coordinated by four carboxylate
oxygen atoms. With the increasing ratio between DMF and
measured in the temperature range of 80−280 K (λ = 324 nm).
3
2
2
2
n
3
2
0.5n
2
2
ex
Notably, the luminescent intensities of 1 and 2 at 80 K are
drastically enhanced compared to those at 280 K, as illustrated in
Figure 8. As the temperatures increase, the emission bands of 1
and 2 are slightly blue-shifted. The above results can be attributed
to the thermally active phononassisted tunneling between the
excited states of low-energy site and the excited states of high-
63
71,72
energy site.
Luminescent Sensing of Aldehyde Vapors. Aldehydes, as
important chemical raw materials and solvents, are very harmful
73
to human health and environment as indoor pollutants.
Thereby, the development of a detection method for aldehydes is
a significant topic in view of environmental and safety
G
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 9. Luminescent intensity and quenching efficiency for the activated 1 (a) and 2 (b) in various aldehyde vapors.
Figure 10. Luminescent intensity and quenching efficiency for the activated 2 upon exposure to benzaldehyde vapor at different time intervals.
7
4
considerations. Among various types of analytical tools for the
hyde (C H CHO), hexanaldehyde (C H CHO), and benzalde-
4 9 5 11
probing of aldehyde vapors, fluorescent sensors have been
considered as a highly sensitive and selective detection method.
Notably, two recently reported lanthanide MOFs [Ln-
hyde (C H CHO). As depicted in Figure 9, the aldehyde vapors
6 5
75
exhibit different degrees of luminescent quenching effects on the
activated 1 and 2. In other words, the luminescent intensities of
the activated 1 and 2 are greatly dependent on aldehyde vapors.
For the activated 1 and 2, the benzaldehyde vapors show the
most quenching effects with the quenching efficiency of 46.7%
and 79.1%, respectively. Thus, the activated 1 and 2 are good
candidates for the recognition of benzaldehyde vapors from
other aldehydes. From the estimated electron numbers by the
(
H DMPhIDC) (H DMPhIDC)] (Ln = Eu, Tb; H DMPhIDC
2 3 3 n 3
=
2-(3,4-dimethylphenyl)-1H-imidazole-4,5-dicarboxylic acid)
show highly sensitive sensing of benzaldehyde-based deriva-
7
3
tives. In this study, the activated 1 and 2 were selected as
luminescent sensors to probe organic aldehyde vapors, such as
formaldehyde (HCHO), acetaldehyde (CH CHO), propional-
3
62
dehyde (C H CHO), butyraldehyde (C H CHO), valeralde-
procedure SQUEEZE, one benzaldehyde and two benzalde-
2
5
3
7
H
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 11. Luminescent intensity and relationship of quenching efficiency versus shift of λ with respect to activated 1 (a) and 2 (b) in various amine
fl
vapors.
Figure 12. Luminescent intensity and quenching efficiency of the activated 2 upon exposure to the aniline vapor at different time intervals.
hyde molecules could be accommodated in the voids of 1 and 2,
respectively. Moreover, the activated samples in various aldehyde
vapors show the same PXRD patterns (Figure S7), indicating
that the activated 1 and 2 are stable in the luminescent sensing
process.
fluorescent spectra upon exposure to benzaldehyde vapor were
measured in different time intervals (Figure 10). Under
benzaldehyde vapors, the luminescent intensity of the activated
2 gradually decreases with increasing time, and the quenching
percentage reaches 73.8% within 10 min (Figure 10). The result
indicates that the activated 2 is a potential solid-state fluorescent
material for sensing of benzaldehyde vapor with a rapid response.
For the sake of testing the luminescent responses of the
activated 2 to the benzaldehyde vapor, the time-dependent
I
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 13. Χ T vs T curves for 3 (a) and 4 (b) in an applied field of 1000 Oe.
m
8
2
Luminescent Sensing of Amine Vapors. The detection of
transitions of the ligands. Notably, the absorption bands of 1
and 2 are almost entirely overlapped by the wide absorption
bands of benzaldehyde and aniline. Obviously, the overlap of the
absorption bands causes a competition for excitation energy
between the analysts (benzaldehyde and aniline) and MOFs,
finally leading to a decrease or even quenching in luminescence
amines is critical in terms of the quality control of food and
76−79
medical diagnosis, and has gained increasing attention.
Hence, the potential of activated 1 and 2 for the sensing of amine
vapors, such as ethylamine (C H NH ), propylamine
2
5
2
(
(
C H NH ), butylamine (C H NH ), diethylamine
3 7 2 4 9 2
83
(C H ) NH), triethylamine (C H ) N), ammonia (NH ·
intensities. This luminescent process corresponds to the ones
previously proposed by other groups.
2
5
2
2
5
3
3
84−87
H O), and aniline (C H NH ), was also explored. As shown in
2
6
5
2
Figure 11, activated 1 and 2 exhibit an obvious decrease in the
luminescent intensity under the amine vapors. The aniline vapor
is the most quenching effective one for activated 1 and 2. The
most quenching efficiencies of aniline reach 55.1% and 85.2% for
activated 1 and 2, respectively, which is much higher than the
second one of triethylamine (Figure 11). Moreover, noticeable
Magnetic Properties. Magnetic susceptibility data of 3 and
4 were collected at 2−300 K in an applied field of 1000 Oe
3
−1
(Figure 13). The χ T value of 3 is 2.76 cm K·mol at 300 K,
m
which is slightly higher than the spin-only value for a high-spin
3
−1 88,89
Co(II) center (S = 3/2, 1.875 cm K mol ).
Upon cooling,
3
χ
T value continuously decreases and reaches to 1.66 cm K
mol at 2 K. The low temperature decrease of the susceptibility
data is attributed to antiferromagnetic exchange interaction
between the Co(II) centers and zero-field interactions. The
χ T value of 4 is 5.70 cm K·mol at 300 K, which is higher than
m
m
−1
shifts of the emission maxima (λ ) in the emission spectra were
fl
also observed. In contrast to the pristine emission peaks of the
90,91
activated 1 (λ = 514 nm) and 2 (λ = 493 nm), apparent blue
fl
fl
3
−1
shifts of 23 and 24 nm were respectively observed for the
activated 1 and 2 exposed to ammonia vapors. Nevertheless,
obvious red shifts of 41 and 20 nm were respectively found for
the activated 1 and 2 upon exposure to ethylamine vapors, as
illustrated in Figure 11. The above observation indicates that the
interactions between amines and ligands/MOFs may trigger
3
−1
3.75 cm K mol expected for two Co(II) centers with an S = 3/
2. Upon cooling, the χ T value decreases monotonically to
92
m
3
−1
0.40 cm K mol at 2 K, demonstrating the presence of
antiferromagnetic interaction between Co(II) centers. The
magnetic susceptibility data of 3 (above 2 K) and 4 (above 20
K) well obey the Curie−Weiss law with Curie and Weiss
80,81
peak shifts and responsive turn off fluorescence.
From the
62
3
−1
constants of C = 2.72 cm K mol and θ = −3.16 for 3, and C =
estimated electron numbers by the procedure SQUEEZE, one
aniline and two aniline molecules could be accommodated in the
voids of 1 and 2, respectively. Moreover, PXRD patterns of the
activated samples in various amine vapors are nearly identical to
the simulated one (Figure S8), suggesting that the structures of
the activated 1 and 2 remained unchanged during the
luminescent sensing process.
3
−1
6
.37 cm K mol and θ = −29.82 for 4 (Figure S10). The
negative Weiss constants also indicate antiferromagnetic
93,94
interactions between the Co(II) centers in 3 and 4.
CONCLUSIONS
■
In summary, four new MOFs were constructed with a new chair-
conformation resorcin[4]arene-based octacarboxylate ligand by
a solvothermal method. They feature diverse motifs and
dimensionalities from the 1D to 3D structures. The fluorescent
sensing studies reveal that 1 and 2 are highly selective and
sensitive fluorescent sensors for aniline and benzaldehyde vapors.
More importantly, 3 and 4 demonstrate a remarkable solvent-
mediated structural transformation from a 1D chain to a 3D
porous framework.
Moreover, the time-dependent fluorescent spectra for
activated 2 were also studied under the aniline vapors. As
illustrated in Figure 12, the luminescent intensities for activated 2
decreased drastically upon exposure to aniline vapors, and the
quenching percentage reaches 79.3% within 10 min. Notably,
after 24 h, the fluorescence quenching percentage of the aniline
vapor is near 85.2%, suggesting that activated 2 is a potential
fluorescent sensor for the aniline vapors.
To explore the fluorescent quenching process toward aldehyde
and amine vapors, the UV−vis diffuse reflectance spectra of 1, 2,
aldehydes, and amines were determined (Figure S9). The UV−
vis absorption bands of both 1 and 2 are located in the range of
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.6b00213.
■
*
S
240−300 nm, which is probably ascribed to π* → π or π* → n
J
DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Diagram of gas sensing equipment, TG curves of 1 and 4,
coordination environment of Co(II) atom in 3, molecular
structures of aniline and benzaldehyde, channel diameters
of 1 and 2, PXRD patterns of experimental ones from
different solvent ratios, PXRD patterns of the activated 1
and 2 after exposed to different aldehyde and amine
vapors, UV absorption spectra of 1, 2, aldehydes and
amines, temperature dependence of χm at 1000 Oe for 3
and 4, FTIR spectra of 1−4, PXRD patterns of 1−4,
emission spectrum of 3 in solid state and selected bond
lengths and angles (PDF)
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AUTHOR INFORMATION
Corresponding Authors
E-mail: yangj808@nenu.edu.cn (J.Y.).
E-mail: songsy@ciac.ac.cn (S.-Y.S.).
■
*
*
*
(
(
E-mail: majf247@yahoo.com. Fax: +86-431-85098620 (J.-
4
873−4877.
F.M.).
(29) Hu, Z. C.; Pramanik, S.; Tan, K.; Zheng, C.; Liu, W.; Zhang, X.;
Chabal, Y. J.; Li, J. Cryst. Growth Des. 2013, 13, 4204−4207.
30) Zhang, H.; Chen, D.; Ma, H.; Cheng, P. Chem. - Eur. J. 2015, 21,
5854−15859.
31) Pablos, J. L.; Vallejos, S.; Mun
F. C.; García, J. M. Chem. - Eur. J. 2015, 21, 8733−8736.
Notes
(
1
(
The authors declare no competing financial interest.
̃
oz, A.; Rojo, M. J.; Serna, F.; García,
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Grant No. 21277022, 21371030,
■
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DOI: 10.1021/acs.cgd.6b00213
Cryst. Growth Des. XXXX, XXX, XXX−XXX