Luminescent sensing and catalytic performances of a multifunctional lanthanide-organic framework comprising a triphenylamine moiety

Article abstract of DOI:10.1002/adfm.201100115

A multifunctional lanthanide-organic framework Tb-TCA (H₃TCA = tricarboxytriphenylamine) comprising a triphenylamine moiety as an efficient luminescence sensitizer is synthesized by a solvothermal method and structurally characterized. Tb-TCA e

Full text of DOI:10.1002/adfm.201100115

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Luminescent Sensing and Catalytic Performances of a
Multifunctional Lanthanide-Organic Framework Comprising
a Triphenylamine Moiety
Pengyan Wu, Jian Wang, Yaming Li,* Cheng He, Zhong Xie, and Chunying Duan*
however, for the optimization of this new
A multifunctional lanthanide-organic framework Tb−TCA (H TCA = tricarbox-
class of lanthanide-organic frameworks for
practical catalysis applications.
3
ytriphenylamine) comprising a triphenylamine moiety as an efficient lumi-
nescence sensitizer is synthesized by a solvothermal method and structurally
characterized. Tb−TCA exhibits lanthanide-based emission (540 nm) and
triphenylamine emission (435 nm) after excitation at 350 nm and works as a
luminescent chemosensor towards salicylaldehyde with a sensitivity of
On the other hand, lanthanide-based
porous metal-organic frameworks are excel-
lent candidates to create multifunctional
materials for chemosensors, provided their
photoluminescence and emission lifetimes
are not influenced by solvent molecules at
ambient conditions. However, as the for-
bidden and faint intraconfiguration f−f tran-
sitions of lanthanide ions results in absorp-
1
0 ppm under optimized conditions. Tb−TCA features a high concentration
of Lewis acid Tb3 sites and Lewis base triphenylamine sites on its internal
+
surfaces; it thus enables both Knoevenagel and cyanosilylation reactions in a
size-selective fashion. The ratiometric fluorescent response towards alde-
hydes (I540/I435) demonstrates that the absorption of the porous material is
size selective, and the interactions between the aldehyde molecules and the
Tb3+ ions play a dominant role in the absorption and activation of the alde-
hyde substrates. In particular, these studies provide opportunities to directly
validate the sorption sites and the catalytic mechanism of the multifunctional
Ln metal–organic framework material by luminescence.
−1
−1 [5]
tion coefficients smaller than 10 M cm ,
targeting porosity and luminescence in a
MOF further restricts the choices of building
blocks, thus, in addition to being able to sus-
tain porosity the ligand should also act as an
[6]
antenna to sensitize Ln ions.
With those parameters in mind, we cre-
ated a multifunctional lanthanide-organic
framework Tb−TCA (H TCA = tricarboxyt-
3
riphenylamine), Scheme 1, through incor-
1
. Introduction
porating a triphenylamine moiety as an efficient luminescence
[7]
3+
sensitizer. We reasoned that the Tb ions exposed on the sur-
face of the framework might serve as potential Lewis acids, and
the triphenylamine located around the cavity of the MOF would
Among the porous polycarboxylate-based metal–organic frame-
works (MOFs),[ the field of lanthanide MOFs (LnMOFs)
with two- or three-dimensional structures is rapidly growing,
because of the discovery of new crystalline structures that
exhibit interesting properties and have potential applications in
catalysis, contrast agents, nonlinear optics, photoluminescent,
and electroluminescent devices.[ One of the extensively inves-
tigated approaches is to immobilize unsaturated Lewis acid Ln
ions within relatively open frameworks with well-defined pores.
This approach enables us to target unique porous LnMOFs with
multifunctional properties and catalytic applications. How-
ever, reports on catalytic studies of lanthanide-organic frame-
works are relatively scarce compared to the large number of
LnMOFs reported,[ especially no experimental data regarding
the catalytic mechanisms in lanthanide-organic frameworks
seems to be available. Such fundamental studies are essential,
1]
[8]
provide a base-like catalyzing force for special reactions. Tb−TCA
was also expected to exhibit bright emission sensitive to the
chemical reactants or products encapsulated, with a ratiometric
response that could be used to examine the roles of the Lewis acid
2]
3+
(
Ln interactions activate sites) and base (triphenylamine inter-
action sites) catalytic forces on the substrates incorporated.
[3]
2
. Results and Discussions
4]
2.1. Synthesis and Characterization of Tb−TCA
The solvothermal reaction of H TCA and Tb(NO ) ·6H O
3
3 3
2
in mixed solvents of dimethylformamide (DMF) and ethanol
gave compound Tb−TCA in a high yield (75%). Elemental
analyses and powder X-ray analysis indicated the pure phase
of its bulky sample. Thermogravimetric analysis (TGA) dem-
onstrated that in the range of 25−200 °C, the TGA curve
exhibited an initial weight loss of 10.9%, corresponding to the
loss of one dimethyl formamide molecule (expected 10.7%),
indicating that the framework of Tb−TCA was stable below
Dr. P. Wu, J. Wang, Y. Li, C. He, Z. Xie, Prof. C. Duan
State Key Laboratory of Fine Chemicals
Dalian University of Technology
Dalian 116012, P. R. China
E-mail: cyduan@dlut.edu.cn; ymli@dlut.edu.cn
DOI: 10.1002/adfm.201100115
2
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observed beside the emission of the triphe-
nylamine group centered about 435 nm. As
can be expected, these luminescences were
strongly quenched (>99% quench percentage)
when salicylaldehyde (SA) was incorporated
(Figure 2) .
To quantitatively investigate the quenching
process, fluorescent measurements were
carried out in a 1 cm quartz cuvette on a sus-
pension of Tb−TCA. The addition of SA to the
suspension of Tb−TCA caused significant lumi-
nescence quenching of both emission bands
and led to an obvious diminishing of the green
emission under UV-light excitation. Under
optimized conditions, the detection limit of the
MOF (4 ppm in CH Cl solution) towards SA
2
2
Scheme 1. Perspective views of channels within multifunctional MOF Tb−TCA showing the
constitutive/constructional fragments
is established at or below 10 ppm (ca. 0.2 mM),
2
00 °C. This property is one of the essential factors for a good
heterogeneous catalyst.
Single-crystal structure analysis reveals the presence of a
non-interpenetrating 3D network comprising one-dimensional
3+
channels. The coordination environment around Tb is shown
in Figure 1. Each terbium ion is coordinated by four oxygen
atoms of four di-monodentate carboxyl groups, two oxygen
atoms of a bidentate carboxyl group, one μ -oxygen atom of
2
another bidentate carboxyl group, and one oxygen atom from a
DMF molecule. The di-monodentate carboxyl groups act as a
four-fold bridge, linking to another Tb3 ion to form a dimeric
unit. This dimeric unit connects neighbors through two centro-
+
symmetric μ -oxygen atoms of the didentate carboxyl groups,
2
forming a one-dimensional pillar along the a axis. These TCA
ligands connected the pillars to form three-dimensional frame-
works with channels along the direction defined by the a axis.
The nitrogen atoms are located around the cavities, providing
base catalyzing forces. It should be noted that the immobiliza-
tion of Lewis-basic sites within porous MOFs, however, has been
a challenge, because such Lewis basic sites tend to bind other
metal ions to form condensed structures. The cross-section
of the running channel is a tetragon consolidated by two centro-
3+
symmetric Tb ions and two TCA ligands with dimensions of
.5 Å × 8.5 Å, which are available for guest accommodation and
7
exchange. The metal centers with removable solvent molecules
are well-positioned in the channels to interact with guest mol-
ecules that enter the framework pores, suggesting that Tb−TCA
should be also an active heterogeneous catalyst for Lewis acid
promoted reactions.[
9]
2
.2. Luminescence and Sensing Studies
Solid state UV–vis absorption spectra of Tb−TCA exhibited
an intense absorption band centered at 350 nm, that can be
Figure 1. View of the crystal packing of Tb−TCA along the a direction
showing the rhombic channels, with exposed coordinated unsaturated
metal ions and nitrogen atoms, and the coordination configuration
of the metal center. Selected bond distances (Å) are: Tb(1)–O(5B)
∗
[10]
assigned to the π−π transition of the triphenylamine group.
Since the triphenylamine emitter is an efficient sensitizer to
2
.276(4), Tb(1)–O(2C) 2.303(4), Tb(1)–O(1) 2.323(4), Tb(1)–
3+
prompt the corresponding luminescence, characteristic Tb
emissions, which can be assigned to the transitions of D → F ,
D → F , D → F , and D → F when excited at 350 nm, are
O(3A) 2.341(4), Tb(1)–O(6E) 2.363(4), Tb(1)–O(4A) 2.378(3), Tb(1)–
O(7) 2.427(4), Tb(1)–O(3D) 2.865(4). Symmetry codes: A. 1–x, 1–y, –z+2;
B. x, 1+y, z; C. –x, 1–y, 1–z; D. x, y, –1+z; E. –x, –y, 1–z.
5
7
4
[11]
3
5
7
5
7
5
7
4
4
4
5
4
6
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Figure 2. Family of luminescent spectra of Tb−TCA emulsion in CH Cl2
2
Figure 3. Fluorescence responses of Tb−TCA upon addition of SA in
upon addition of various amounts of salicylaldehyde (SA) up to 2 mM.
The insert showing emission intensities at 540 nm as a function of SA in
the lower concentration range (10 to 30 ppm). Excitation at 350 nm.
CH Cl at 540 nm (square marks) and at 435 nm (dot marks). Excitation
2
2
at 350 nm. The inset shows the quenching effect coefficients (KSV) of SA
at the above-mentioned emission bands, excited at 350 nm. The values
I0 and I represent the luminescence intensities of aldehyde-free Tb−TCA
and aldehyde-incorporated Tb−TCA, respectively.
and the reduction in luminescence intensity is proportional to the
concentration of the aldehyde.
The quenching effect is rationalized by the Stern–Volmer
probe environment, and excitation intensity) by self-calibration
of two emission bands.
equation:[
12]
[14]
I
0
I = 1 + KSV[M]
2
.3. Knoevenagel Condensation Reaction Catalyzed
The values I and I are the luminescence intensities of alde-
0
by Tb−TCA Materials
hyde-free Tb−TCA and aldehyde-incorporated Tb−TCA, respec-
tively, [M] is the molar concentration of the aldehydes added,
and KSV is the quenching-effect coefficient of the aldehyde.
KSV was calculated from the experimental data for the exam-
ined aldehyde. The high quenching effect coefficient (KSV) of
Inspired by the very few example of porous MOFs with Lewis-
basic sites including amides sites,
tion, which requires the formation of an anion of the active
methylene-containing basic compound,
light the significance of the functional properties of Tb−TCA.
As shown in Table 1, the loading of a molar ratio of only 2%
[
15]
the Knoevenagel reac-
[
16]
−1
was used to high-
ca. 2400 M and the low detection limit for SA allowed us to
easily identify the existence of a small amount of aldehyde in
solution. And since the emission wavelength is hardly varied
during the addition of SA, the fluorescence-quenching effect of
the aldehydes was ascribed to a photo-induced energy transfer
Table 1. Knoevenagel reaction of salicylaldehyde derivatives with
malononitrile catalyzed by Tb−TCA. Reaction conditions: malononitrile:
(
PET) mechanism from the guest molecules to the excited state
1
.2 mmol, aldehyde: 0.5 mmol, Tb−TCA catalysts: 0.01 mmol (2 mol%);
[13]
of the triphenylamine groups.
room temperature for 6 h.
Interestingly, KSV values referring to the intensities at 435 nm
triphenylamine emission) and at 540 nm (the Tb emis-
3
+
CN
NH
(
O
Tb-TCA
CH2Cl2
R
+ NC
CN
R
sion) are different (Figure 3). With the decrease of the inten-
sities of the two emission bands upon incorporating SA, the
I540/I435 ratio increases significantly, since the two emission
OH
O
Substrate
Conversion (%)a)
99
3
+
bands were isogenous, and the characteristic Tb emission
was prompted by the excitation of the triphenylamine group.
The quenching of the two emission bands was attributed
to PET from the triphenylamine group to SA, whereas the
increase of the I540/I435 ratio should be attributed to the inter-
O
OH
23
3
+
actions between SA molecules and Tb ions. Accordingly,
the enhancement of the emitting efficiency at 540 nm (Tb3
characteristic emission) was attributed to the replacement of
the coordinated solvent molecules by aldehydes. The potential
of luminescent MOFs for sensing functions was proposed a
decade ago; however, this emerging ratiometric chemosensor is
very significant, as it can eliminate most or all ambiguities (i.e.,
canceling artifacts due to variations in probe concentration,
O
+
OH
<2
N
O
OH
a)Conversion based on aldehydes.
2
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of Tb−TCA lead to over 90% conversion of salicylaldehyde.
The catalysis efficiency of Tb−TCA was comparable to the best
results obtained previously for MOFs, a yield of 98% obtained
after 12 h.[ In contrast, the conversion yield for 2-hydroxy-
of the substrate in the channels of the MOFs through interac-
tions between the Tb3 ions and the C=O group of the alde-
hydes. It seems that, beside the base-type triphenylamine
+
15]
3+
catalytic active sites, the interactions between SA and the Tb
1
8
-naphthaldehyde (NSA), with molecular dimensions of 9.7 Å ×
ions also exhibited excellent activities for this kind of Kno-
evenagel condensation. While a series of MOFs can catalyze
the important reactions through isolated acid and/or base
catalyzing forces, the incorporation of both acid- and base-
catalyzing forces within one channel is quite rare. The highest
yield achieved in the channels demonstrates their significant to
directly enhance the catalytic efficiency.
.4 Å,[ is reduced to about 20%, under similar experimental
17]
conditions. The presence of 5-(diethylamino)salicylaldehyde
DSA) only causes a trace conversion under the same experi-
[21]
(
mental conditions. One would expect a comparable reactivity,
thus this experiment suggests that the 8.5 Å wide section in
Tb−TCA is too small to accommodate the transition-state geom-
etry required for activating these substrates, indicating that the
activation of the carbonyl species occurs inside the channels,
not on the surface of the solid catalyst. Since the Knoevenagel
reactions could not take place in the absence of the catalyst
Tb−TCA, this set of experiments demonstrates that Tb−TCA is
a real catalyst with at least the aromatic aldehydes accessing the
catalytic sites via the cavity.
To confirm the selective accommodation and activation of
reactants by Tb−TCA, adsorption experiments were performed.
Adding Tb−TCA (50 mg) to a dichloromethane solution con-
taining substrates and stirring for 12 h afforded new crystalline
solids. These crystalline solids are difficult to dissolve in any
solvent, thus deuterium chloride was used to destroy the MOF
Furthermore, the luminescent responses for these aldehydes
are size-selective. As shown in Figure 5, the addition of 2-NSA
and DSA reduced the luminescence of the Tb3 (540 nm)
and triphenylamine (435 nm) emissions of the suspension of
Tb−TCA in CH Cl , while the ratio (I540/I435) of the two emis-
+
2
2
sion intensities did not vary significantly, since the two emission
bands were isogenous, and the characteristic Tb3 emission
was prompted by the excitation of the triphenylamine group.
The quenching of the two emission bands whilst maintaining
the ratio (I540/I435) suggested the absence of obvious interac-
tions between NSA or DSA and the lanthanide ions. In accord,
structural simulations of the substrates demonstrated that the
rhombic channels were not large enough to encapsulate mole-
cules of NSA or DSA.
+
1
structure in order to increase their solubility. H NMR spectra
(
Figure 4) show that Tb−TCA adsorbed 3, 1, and 0.8 equivalents
These results all supported that only molecules with suitable
sizes have the potential to enter the channels and to interact
with the Ln sites, which thus exhibited a size-selective lumines-
cent response. The Lewis-acid Ln sites played a dormant role
in the Knoevenagel condensation reactions. Although only a
few lanthanide–organic frameworks could be used as efficient
catalysts to prompt special interactions, the validation of the
catalytic mechanism of the reactions via rati-
ometric luminescent responses is very sig-
nificant. The new approach can be extended
to other reactions prompted by Lewis-acid-
and/or base-catalyzed forces for sensing and
absorbing organic molecules in environ-
mental or organic-synthetic applications.
of SA, NSA and DSA per triphenylamine moiety, implying that
the smaller molecule was more easily introduced to the channels
of Tb−TCA. Infrared spectroscopy of the catalyst impregnated
with a CH Cl solution of the reaction solution revealed a C=O
2
2
−1
−1
stretch vibration at 1687 cm . The red shift from 1708 cm
free aldehyde) suggested the sorption of SA and the activation
[4]
(
2
.4. Cyanosilylation Reaction Catalyzed
by Tb−TCA Materials
Since the addition of cyanide to a carbonyl
compound to form a cyanohydrin is one
of the fundamental carbon–carbon bond-
forming reactions in organic chemistry
and has frequently been at the forefront of
[18]
advances in chemical transformations,
a
cyanosilylation reaction was performed with
a 1:2.4 molar ratio of the selected 2-nitroben-
zaldehyde (2-NBA), 3-nitrobenzaldehyde
(
1
3-NBA),
-naphthylaldehyde(1-NTA), and cyanotri-
methylsilane in CH Cl at room temperature
4-nitrobenzaldehyde
(4-NBA),
Figure 4. a ) 1H NMR spectra of the powder Tb−TCA that decomposed in DCl:DMSO-d6.
1
2
2
b–e) H NMR spectra of the powder Tb−TCA with guest molecules adsorbed that decomposed
through a heterogeneous manner. As shown
in Table 2, the presence of 2 mol% solid
Tb−TCA led to over 75% conversion 2−NBA,
in DCl:DMSO-d : malononitrile (b), 5-(diethylamino)salicylaldehyde (DSA) (c), 2-hydroxy-1-
6
naphthaldehyde (NSA) (d), and salicylaldehyde (SA) (e), respectively. The peaks marked with
asterisks represent the signals of protonated TCA.
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T a b le 2 . Catalytic cyanosilylation of carbonyl substrates in the pres-
ence of Tb−TCA. Reaction conditions: (CH ) SiCN: 1.2 mmol, aldehyde:
3
3
0
.5 mmol, Tb−TCA catalysts: 0.01 mmol (2 mol%), room temperature
under N for 4 h.
2
O
Tb-TCA
CH2Cl2
OSi(CH3)3
CN
(CH3)3SiCN
Ar
H
Ar
Substrate
CHO
NO
Conversion (%)a)
7
8
2
5
9
CHO
2
O N
4
7
O2N
CHO
CHO
11
a)Conversion based on aldehydes.
luminescence behavior of Tb−TCA enabled us to validate the
sorption properties of the MOFs and, at the same time, to
distinguish between possible mechanism of these catalytic
reactions.
Figure 5. a) Luminescence responses of Tb−TCA to the addition of
aldehyde (0.1 mM). Intensities were recorded at 540 nm, excitation at
3
. Conclusions
3
50 nm. b) The I540/I435 ratio of Tb−TCA–CH Cl emulsion, blank and
2 2
after sorption of different SAs (0.1 mM). Excitation at 350 nm.
In summary, we reported a new approach to create a multifunc-
tional lanthanide–organic framework Tb−TCA that features a
high concentration of Lewis-acidic Tb3 sites and Lewis-basic
triphenylamine sites on its internal surfaces. Tb−TCA can
catalyze both the Knoevenagel reaction and cyanosilylation in
a size-selective fashion through base-type and acid-type catal-
ysis sites, respectively. Further, it exhibites bright lanthanide-
based emission simultaneously with the direct emission of
triphenylamine. The new approach will be extended to other
lanthanide-based MOFs with other luminescent-active lan-
thanide ions and a series of amino-containing organic dyes
to assembly more efficient acid- and/or base-type MOF-based
catalysts and luminescent materials for sensing or absorbing
organic molecules towards environmental and organic-
synthetic applications.
1
monitored by H NMR. The catalysing efficiency of Tb−TCA was
+
[19]
comparable to the best results previously obtained for MOFs,
a yield of 98% obtained after 16 h, and represents a significant
improvement compated to lanthanide bisphosphonates MOFs
with a yield lower 70% after 16 h.[ Most notably, the use of
20]
2
-NBA, a potentially bidentate substrate, resulted in a higher
catalytic efficiency. As shown in Table 2, our experiments show a
0% increase in the yield of 2−NBA compared to that of 3−NBA
2
under the same experimental conditions.
It is important to note that the sorption of 2−NBA caused
the luminescence quenching of the two bands, and at the
same time led to a two-fold increase in the ration (I540/I435) in
comparison to free Tb−TCA, while in the presence of 4-NBA
and 3-NBA the change in the ratio (I540/I435) was only minor
(
Figure 6). The interactions between 2−NBA and Tb−TCA
might be similar to that of SA, for which the guest molecules
acted as bidentate chelators to coordinate Tb . Molecules of
4
. Experimental Section
3
+
Material and Methods: All chemicals were of reagent-grade quality
3
−NBA are unlikely to react as bidentate chelators and thus
obtained from commercial sources and used without further purification.
3
+
cannot replace the coordinating solvent molecules on Tb
1
H NMR spectra were recorded on a Varian INOVA 400M spectrometer.
as easily. These results demonstrated that the interactions at
Powder XRD was performed on a Riguku D/Max-2400 X-ray diffractometer
with a Cu sealed tube (λ = 1.54178 Å). Elemental analyses were obtained
with an Elemental Analyzer Vario EL ? instrument. Thermogravimetric
3
+
the Tb sites were dominant for ratiometrical luminescent
responses and for activating the aldehydes. In this case, the
2
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ligand backbones were refined anisotropically. Hydrogen atoms within
the ligand backbones were fixed geometrically at calculated positions
and allowed to ride on the parent non-hydrogen atoms. Hydrogen atoms
of the carboxylate moieties were found from the difference Fourier maps
and refined with the isotropic parameters fixed as 1.5 times of those
oxygen atoms they were attached to and with a fixed O−H distance fixed
of 0.85 Å.
Typical Procedure for Knoevenagel Reactions Using the Catalyst Tb−TCA:
To a mixture of malononitrile (1.2 mmol) and aromatic aldehyde
(0.5 mmol), Tb−TCA (2 mol%) was added. The resulting mixture was
stirred at room temperature for 6 h. The reaction was monitored by thin-
layer chromatography (TLC). Conversion was determined by 1H NMR
analysis.
Typical Procedure for Asymmetric Cyanosilylation of Aldehydes Using
the Catalyst Tb−TCA: To a mixture of TMSCN (1.2 mmol) and aromatic
aldehyde (0.5 mmol), Tb−TCA (2 mol%) was added. The resulting
mixture was stirred at room temperature for 4 h. The reaction was
1
monitored by TLC. Conversions were determined by H NMR analysis.
Acknowledgements
We gratefully acknowledge financial support from the NNSF (Number:
2
1025102).
Received: January 17, 2011
Revised: February 15, 2011
Published online: May 31, 2011
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2
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Synthesis and Crystal Growth: Tb−TCA:
A
mixture of
21]
4
,4′,4″-tricarboxytriphenylamine[ (H TCA) (94 mg, 0.25 mmol) and
3
Tb(NO ) · 6H O (453 mg, 1 mmol) were dissolved in 15 mL mixed
3
3
2
solvents of dimethyl formamide (DMF) and ethanol in a screw-capped
vial. The resulting mixture was kept in an oven at 100 °C for 3 days.
Yellow block-shaped crystals were obtained after filtration. Yield: 75%.
Anal. calcd. for C H N O Tb (%): C, 47.73; H, 3.86; N, 6.18; Found: C,
2
7
26
3
8
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4
7.77; H 3.80, N 6.08.
Crystallography of Tb–TCA: C H N O Tb, M = 679.43, triclinic,
2
7
26
3
8
space group P-1, a = 8.257(6) Å, b = 13.163(10) Å, c = 14.238(11) Å,
3
α = 114.261(8), β = 96.493(9), γ = 101.699(9), V = 1347.6(17) Å , Z =
−3
−1
2
, Dc = 1.674 g cm , μ(Mo-Kα) = 2.68 mm , T = 293(2) K. 4583 unique
reflections [Rint = 0.0676]. Final R [with I > 2σ(I)] = 0.0446, wR (all data) =
1
2
[
0
.0741, GOOF = 1.028. CCDC 807487 contains the supplementary
crystallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif. Intensities were collected on a Bruker
SMART APEX CCD diffractometer with graphite monochromated Mo-Kα
(
λ = 0.71073 Å) using the SMART and SAINT programs. The structure
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2
was solved by direct methods and refined on F by full-matrix least-
squares methods with SHELXTL version 5.1. Non-hydrogen atoms of the
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