A stable luminescent zinc-organic framework as a dual-sensor toward Cu2+ and Cr2O72-, and excellent platform-encapsulated Ln3+ for systematic color tuning and white-light emission

Article abstract of DOI:10.1039/c9nj02861g

A stable, luminescent zinc-organic framework (MOF)[Zn(OBA)₂(PTD)·2DMF·2H₂O]_n (1; H₂OBA = 4,4′-oxybis(benzoic acid), PTD = 6-(pyridin-4-yl)-1,3,5-triazine-2,4-diamine) was synthesized using a V-shaped, carboxylate H₂OBA ligand containing conjugated π-moieties and a rigidly auxiliary N-rich PTD ligand, which displayed a 3D, three-fold interpenetrated framework with highly thermal and chemical stabilities. Complex 1 exhibited a strong luminescent emission, and could selectively detect Cu²⁺ and Cr₂O₇^2-, making it a potential dual functional chemosensor. Furthermore, the systematic explorations of lanthanide(iii) cation encapsulation for compound 1 suggested that Ln³⁺-doped compounds are good candidates as color-tunable and barcoded materials. Moreover, by soaking this as-synthesized MOF (50 mg) into a 10 mL DMF solution containing 5 × 10^-5 mmol Ln³⁺ ions (Eu³⁺/Tb³⁺, 13/7), the white light-emission of the Ln³⁺-doped compound 1 was realized with the Commission Internationale de L'Eclairage coordinates (0.3095, 0.2945). The quantum yield of this white light-emitting sample is 29%, which is higher than those of most reported doped MOFs with white light-emission. Furthermore, compound 1 exhibited a selective gas capture for CO₂ over CH₄.

Full text of DOI:10.1039/c9nj02861g

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Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
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A stable luminescent zinc-organic framework as dual-sensor
2-
toward Cu2+ and Cr2O7 , and excellent platforms encapsulated
Ln3+ for systematic color tuning and white-light emission
Received 00th January 20xx,
Accepted 00th January 20xx
Bo-Wen Qin, Xiao-Ying Zhang* and Jing-Ping Zhang*
DOI: 10.1039/x0xx00000x
A stable luminescent zinc-organic framework (MOF) [Zn(OBA)2(PTD).2DMF.2H2O]n (1; H2OBA = 4,4′-oxybis(benzoic acid),
PTD = 6-(pyridin-4-yl)-1,3,5-triazine-2,4-diamine) has been synthesized by using V-shape carboxylate H2OBA ligand
containing conjugated
π moieties and rigidly auxiliary PTD ligand with N-rich, which displays a 3D three-fold
interpenetrated framework with highly thermal and chemical stabilities. Complex 1 exhibits a strong luminescent emission,
and can selectively detect toward Cu2+ and Cr2O72-, making it be a potential dual functional chemosensor. Furthermore,
systematic explorations of lanthanide(III) cation encapsulation for compound 1 have implied that the Ln3+-doped
compounds are good candidates as the color-tunable and barcoded materials. Moreover, by soaking this as-synthesized
MOF (50 mg) into 10 mL DMF solution containing 5*10-5 mmol Ln3+ ions (Eu3+/Tb3+, 13/7), white light-emission of Ln3+-
doped compound 1 was realized with the Commission International de I’Eclairage coordinate (0.3095, 0.2945). The
quantum yield of this white light-emitting sample is 29%, which is higher than those of most reported doped MOFs with
white light-emission. Besides, compound 1 exhibits a selective gas capture for CO2 over CH4.
health effects and the extensive use raises various
environmental concerns.10 Thus, exploring of the
environmentally friendly materials superseding mercury-
Introduction
Cu2+ is one of the most important and essential elements in
biological systems.1 Deficiency or excess of Cu2+ can cause
disease to living bodies.2 The massive use of Cu2+ ions in
industry has resulted in severe water pollution.3 Meanwhile,
contained fluorescent lighting is well needful.
Metal-organic frameworks (MOFs) containing tunable
structure and high porosity exhibit potential applications in gas
storage, catalysis, chemical sensing, luminescence and so on.11-
2-
Cr2O7 generated from industrial production such as pigment
15
Among them, the multifunctional MOFs incorporated multi-
manufacturing, leather tanning, and chromium plating, is one
of the toxic heavy-metal water pollutants and classified as a
Group “A” carcinogen for human bodies.4 However, the
currently detection methods for these ions are mainly based
on instruments with high-cost and trained personnel.5
Therefore, it is imperative and desired to develop cost-
effective and selective materials to simultaneously realize the
excellent detection of Cu2+ and Cr2O72- ions. On the other hand,
materials producing high-intensity white light are widely used
applications in different fields have attracted much attention
since they can be used in more extensive domains and
mitigate multiple issues mentioned above.12, 16-18 Therefore, a
rationally designing strategy towards multifunctional MOFs is
crucial. In this regard, the mixed-ligand strategy has been an
effective strategy to construct MOFs with specific
application.19 Liu et al. synthesized
a
Zn2+-MOF as
chemosensor for high-efficiency detection of nitrobenzene
using 2,6-naphthalenedicarboxylic acid and 1H-tetrazol-5-
amine.20 Das and co-workers reported a stable 3D microporous
Co2+-MOF based on 4,4’-oxybis(benzoic acid) and 3,3’-
azobis(pyridine), exhibiting highly selective CO2 separation
under ambient conditions.21
In this work, we selected V-shape carboxylate ligand 4,4′-
oxybis(benzoic acid) (H2OBA) and rigid N-rich auxiliary ligand 6-
(pyridin-4-yl)-1,3,5-triazine-2,4-diamine (PTD) to design the
desired multifunctional MOF according to the following
reasons: (1) The V-shape ligand can distort to adopt a variety
of coordinated configurations, and carboxylate groups have
various coordination modes;22, 23 (2) The rigid N-rich auxiliary
7
in daily lighting and large-panel.6, A generally adopted
approach to obtaining this material has been to blend together
materials that can emit red, green, and blue.8 However, this
mix is also blind and tentative.9 Furthermore, mercury-
contained fluorescent lighting is one of the most extensively
used white-light sources, but the mercury can cause adverse
ligand with high basicity can improve the stability of MOFs by
25
enhancing the coordination bond strength;24,
(3) Amino
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groups introduced to MOFs may act as sensing sites for special poured into deionized water (300 mL) and stirred for 30
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metal ions and anions;20 (4) The aromatic organic linkers with minutes. The white precipitate was washDeOdI:w1i0t.h10c3o9l/dC9HN2JO02a8f6t1eGr
conjugated π moieties can efficiently promote the luminescent separated by filtration, and then dried under vacuum to yield
26
intensity.22,
Moreover, luminescent MOFs can act as a PTD ligand (3.63 g, 18.15 mmol, 91% yield based on 4-
platform to exhibit mono- or bi-modal luminescence by cyanopyridine). 1H NMR (600 MHz, DMSO): δ = 8.71 (dd, J = 4.8,
encapsulating extra-framework lanthanide(III) ions on the 1.2 Hz, 2H), 8.07 (dd, J = 4.8, 1.2 Hz, 2H), 6.93 (d, J = 32.4 Hz,
basis of the size-exclusion effect, which can be used as barcod 4H), (Fig. S1).
and color-tunable materials.12, 27 More importantly, doping the Synthesis of [Zn(OBA)2(PTD).2DMF.2H2O]n (1)
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framework structures with Ln3+ ions (for example, Eu3+ and
A mixture of Zn(NO3)2·6H2O (1 mmol, 0.3000 g), H2OBA (0.5
Tb3+) by a special concentration may also result in white-light
mmol, 0.1290 g) and PTD (0.5 mmol, 0.0900 g) in 8 mL mixture
emitting MOFs.10,
Taking inspirations from above
28
solvents of DMF/CH3CH2OH (v/v, 5/3) was given into a 23 mL
Teflon−lined stainless steel autoclave and heated under
autogenous pressure at 80°C for 68 h. After cooling down to
room temperature, colorless octahedral crystals of compound
considerations,
a
stable luminescent Zn-MOF, namely
[Zn(OBA)2(PTD).2DMF.2H2O]n
(1
), was synthesized and
possesses excellent thermal and chemical stabilities.
Compound
exhibits noteworthy chemosensing towards Cu2+
1
1
were harvested (yield: 71%, based on zinc). Elemental
2-
and Cr2O7 ions by the detailedly luminescent experiments.
After doping Ln3+ ions (Eu3+ and Tb3+) into this MOF with
different proportions and concentrations, the doped
analysis calcd (%) for C42H42N8O14Zn (948.22): C 53.20, H 4.46,
N 11.82; found: C 52.96, H 4.59, N 11.97.
Crystal structure determination
compound
1 exhibits multiband emissions and can be applied
The intensity data were collected by an Oxford Diffraction
Gemini R Ultra detector diffractometer equipped with the
graphite monochromated Mo Kα radiation (λ = 0.71073 Å) at
293 K, using the ω scan technique. The structure was solved by
direct methods and all the non−hydrogen atoms were refined
anisotropically on F2 by full−matrix least−squares using SHELXL
package.30 H atoms were introduced into calculated positions.
The PLATON SQUEEZE treatment was applied because all guest
solvent molecules are extremely disordered and cannot be
modeled.31 Crystallographic data collected and crystal
structure refinement were summarized in Table S1. We also
showed the selected bond lengths and angles in Table S2. Full
crystallographic data have been stored with the CCDC
(1815429).
as color-tunable and barcoded luminescent materials.
Furthermore, upon excitation at 283 nm, the Eu3+/Tb3+ co-
doped MOF with a special concentration can emit white light
with a quantum yield of 29%, which maybe a promising
material to replace the mercury-contained fluorescent
lighting.10
EXPERIMENTAL SECTION
Materials and General Methods
All commercially available reagents used were AR grade and
used as received. The PTD ligand was synthesized according to
the method reported earlier with little modulation.29 1H NMR
spectra were recorded on
a Varian Mercury Vx-300
Encapsulation of lanthanide(III) cations into compound 1
spectrometer. Powder X-ray diffraction (PXRD) were
performed over the 2θ range of 5° to 30° on a Rigaku D/Max-
2500 diffractometer using Cu Kα (λ = 1.54184 Å) radiation and
a graphite monochromator at room temperature. Elemental
analyses (EA) for C, H and N were conducted using an
Elementar Vario EL analyzer. Thermogravimetric analyses (TGA)
were carried out using a Rigaku PTC-10ATG-DTA analyzer at a
heating rate of 10°C min−1 under nitrogen atmosphere from
room temperature to 800oC. Gas adsorption measurements
were performed on a Micromeritics ASAP 2020 M gas
adsorption analyzer. X-ray photoelectron spectra were
recorded on an Axis Ultra DLD X-ray photoelectron
spectroscopy of Kratos Analytical Ltd. The photoluminescent
Freshly prepared compound
1 (50 mg) was added in DMF
solutions of lanthanide nitrates with different molar ratios of
Eu3+/Tb3+: 1:0, 0.6:0.4, 0.4:0.6, 0.2:0.8 and 0:1 (totally, 1 mmol
in 10 mL DMF), respectively. After one days of soakage, the
crystals were washed with DMF to remove residual
lanthanide(III) cations on the crystal surface.
Activation of compound 1
The as−synthesized compound
1 was washed with DMF
solution and soaked for 3 days in acetone with changing the
solvent per 24 hours. Afterwards, the sample was filtrated and
dried in vacuum oven at 175oC to remove the free solvent
molecules. Finally, the activated compound
(Fig. S2).
1 was obtained
properties were measured using
a FLSP920 Edinburgh
Fluorescence Spectrometer and a slit width of 1.0 nm. The
quantum yield was measured employing the integrating
sphere method.
RESULTS AND DISCUSSION
Synthesis of the PTD ligand
Crystal Structure
A mixture of 4-cyanopyridine (2.08 g, 20 mmol), dicyandiamide Single-crystal X-ray diffraction analyses revealed that
(2.10 g, 25 mmol) and potassium hydroxide (0.22 g, 4 mmol) compound belongs to orthorhombic crystal system with the
was added to a round bottom flask with 1,2-dimethoxyethane space group Fdd2. As shown in Fig. 1a, the asymmetric unit of
(20 mL). Then the solution was heated to reflux for 5 h. After compound is composed of two independent Zn(II) cations,
cooling to ambient conditions, the reaction contents were four OBA2- ligands and one PTD ligand. Each Zn(II) cation shows
1
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Fig. 1 Crystal structure of compound 1. (a) The coordination geometry of the paddle-wheel Zn2O8N2 unit; (b) A single 3D framework of compound 1 and the 1D
channels; (c) Space-filling model of the 3D framework, showing the 1D channels; (d) Schematic illustration of the three -fold parallel interpenetrated topology. The
hydrogen atoms have been omitted for clarity. Color codes: C in light grey, O in red, N in blue, Zn in turquoise. Symmetry code: A, -0.25+x, 0.75-y, 0.25+z.
a square-pyramidal coordination geometry by coordinating ligand and PTD ligand can be regarded as a two-connected
with four oxygen atoms belonging to four individual OBA2- linker, respectively (Fig. S3). Thus the 3D framework of
ligands and one nitrogen atom from a PTD ligand. The Zn-O compound
1
displays a six-connected uninodal net with the
and Zn-N bond lengths are falling in the range of 2.002-2.084 Å short Schläfli symbol of 36
. .
66 73 by using the software package
and 2.057-2.079 Å, respectively, well corresponding with those of TOPOS 4.0 (http://www.topospro.com) (Fig. 1d).33 After
reported in the previous literatures.32 Two adjacent Zn(II) removal of solvent molecules filled in the channels, the
centers with the distance of 2.985 Å are linked by four accessible volume of compound
carboxylate groups of four OBA2- ligands, forming by PLATON.31
1 is then calculated to be 47.6%
a
conventional paddle-wheel second building unit (SBU). The bis- Chemical stability
bidentate H2OBA ligand is a bent linker with the dihedral angle
The measured PXRD pattern of compound
coincident with that of the simulated pattern derived from the
crystal data, confirming the phase purity of compound (Fig.
S4). The TGA curve reveals that complex (Fig. S5) is thermally
stable even if heated to 300oC, which was also confirmed by
the PXRD pattern of compound
heated for 4 hours at 300oC
(Fig. S6). Upon further heating, the organic framework of
compound begins to collapse. The PXRD patterns shown in
Fig. S7 suggest that complex can maintain its stability after
1 is almost
of 71.64o between two phenyl rings. As shown in Fig. 1b, the
neighboring Zn2O8N2 paddle-wheel SBUs are bridged by OBA2-
and PTD ligands, forming the 3D framework. The PTD ligands
paralleling the ab plane segment the big quadrangular
channels to generate two kinds of channels: a hexagonal and a
triangular aperture, respectively (Fig. 1b). The big hexagonal
prism channel has a dimension of 18.2 Å while the effective
size of small triangular prism channel is 6 Å. Though a single 3D
framework contains two different channels along the c
direction, three identical 3D networks are interlocked with
each other to construct a three-fold parallel interpenetrated
3D→3D→3D framework containing a 1D quadrangular channel
with a size of 4.9 Å (Fig. 1c). A better discernment into the
nature of this interpenetrated 3D framework can be realized
by application of the topological approach. According to the
topological point of view, the Zn2O8N2 paddle-wheel SBUs can
be viewed as a six-connected node. Meanwhile, the OBA2-
1
1
1
1
1
being immersed in different boiling solvents for 36 hours,
including n-hexane, ethyl acetate, ethanol and toluene. It is
believed that the exceptional stability of compound
1 is
primarily attributed to the strong metal-N bonds as
predesigned, the rigid OBA2- pillars and the three-fold
interpenetrated network.32 The grand stability of compound
1
ensures its retained structure during functional exploration
and thus builds an excellent basis for further application.
Luminescent sensing properties
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MOFs constructed by d10 metals and conjugated organic the potential of compound
ligands have received considerable attentions because of their emission intensity gradually decreases as the concentration of
hopeful application as luminescent sensors.16, 20, 25, 34 The solid- Cu2+ increases and the decline of intensity can still be observed
state photoluminescent spectra of PTD ligand, H2OBA ligand as the Cu2+ concentration is decreased to 10−6 M (Fig. S12). The
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for the sensing of Cu2+ ions. The
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DOI: 10.1039/C9NJ02861G
and compound
1 were recorded under ambient conditions (Fig. detection limit of compound 1 is 4.43 μM calculated according
S8 and S9). PTD and H2OBA ligands show emissions at 449 nm to the linear relationship between fluorescence response and
(λex = 375 nm) and 563 nm (λex = 346 nm), respectively. Upon the concentration of Cu2+ (Fig. S13).26 The anti-interference
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excitated at 380 nm, compound
1 displays an emission peak at sensing of compound 1
for Cu2+ ions was further explored by
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490 nm, which might be mainly attributed to the PTD ligand on the competing experiments. Generally, we carried out these
account of their similar emission peaks.35 More importantly, tests in the same conditions as the above sensing experiments,
the inspiring structural feature is the presence of Lewis basic except DMF solution (10 mL) containing mixed metal ions
sites of free N-atoms in the pores, which supports to binding (each 10 mM) instead of the single metal solution. The results
other metal cations.3 Therefore, the as-synthesized compound suggest that the compound
1
can detect Cu2+ ions with high
1
(50 mg) was added into 10 mM DMF solutions (10 mL) of selectivity even in the existence of other metal ions (Fig. S14).
-
M(NO3)X (M = Na+, Cr3+, Mg2+, Ni2+, Mn2+, Co2+, Cu2+, Zn2+, or
Simultaneously, the effects of various anions (NO3 , Cl-, Br-, I-,
Cd2+). The metal ion-incorporated samples as microcrystalline SO42-, CH3COO-, OH-, ClO4 , C6H5COO-, NO2 , Cr2O72-; 10 mM) on
-
-
solid were isolated by filtration and dried at 50oC for 12 hours luminescent intensity of compound
1 were also evaluated (Fig.
for luminescent studies, in which the frameworks are S15 and S16). As shown in Fig. 2b, the luminescent intensities
invariable (Fig. S10). Interestingly, it is found that Zn2+ ions of the different anion-incorporated samples are closely related
have a negligible effect on the luminescence intensity of to anion species. There is
complex , while other metal ions lead to varying degrees of luminescent intensity when Cr2O7 anions were incorporated
quenching to the luminescence. Among them, Cu2+ ions cause into the framework of compound
, suggesting that compound
a significant diminution of
2-
1
1
2-
a most significant quenching effect (Fig. 2a and S11), indicating
1 may be a MOF sensor for Cr2O7 ions. To further assess the
2-
sensitivity of compound
1 toward Cr2O7 ions, the DMF
solvents containing different concentration Cr2O7 anions
were used to carry out this experiment. The results indicate
2-
Fig. 3 High-resolution XPS spectra for the N1s region of compound
1 -
(a) and Cu2+
Fig. 2 The comparisons of luminescent intensities of compound
1 treated with 10
incorporated sample (b).
mM various cations (a) and anions (b) in DMF solutions for 24 h.
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can effectively probe Cr2O72- anions with the corresponding to the only Eu3+- and Tb3+-doped samples (Fig.
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concentration as low as 10-5 M (Fig. S17). The detection limit 4a and 4c), respectively. Besides, co-dDoOpeI:d10.s1a0m39p/Cle9sNJe0x2h86ib1Git
2-
value towards Cr2O7 is 90.4 μM simulated by Stern-Volmer their multiband emissions (Fig. 4b and S20). The samples
equation (Fig. S18).26
doped by using different molar rations of Eu3+ and Tb3+ with a
To illuminate the possible mechanism for the quenching total of 1 mmol had Commission International de I’Eclairage
effect of Cu2+ ions, N1s X-ray photoelectron spectroscopy (XPS) (CIE) coordinates of (0.3413, 0.5767), (0.4328, 0.4992), (0.5002,
spectra were measured on compound
sample (Fig. 3). The N1s core-level spectrum of compound
1
and Cu2+-incorporated 0.4395), (0.5587, 0.387) and (0.6316, 0.335), suggesting the
9
1
CIE coordinates can be adjusted by quantitatively changing the
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presents a broad peak at 399.9 eV, which matches well with Eu3+/Tb3+ molar rations (Fig. 5a). It is noteworthy that both
two peaks at 399.1 and 400.05 eV. The two peaks can be Eu3+- and Tb3+-doped samples show very long luminescence
assigned to the uncoordinated and coordinated N atoms from Ln3+ lifetimes (τ1 = 530.6851 μs and τ2 = 1221.9450 μs for Eu3+;
PTD linker, respectively.4, 36 After incorporated with Cu2+ ions, τ1 = 813.8381 μs and τ2 = 1673.1261 μs for Tb3+), while the
a new N1s peak arises at 406.8 eV, suggesting the chelating luminescence lifetimes of Eu3+/Tb3+-codoped specimens are
interaction between the uncoordinated N atoms and Cu2+ ions. relatively short (τ1 = 532.2680 μs and τ2 = 1500.8012 μs for
This coordination behavior makes the N atoms of amino Eu0.2/Tb0.8; τ1 = 612.6855 μs and τ2 = 1428.0812 μs for
groups of PTD ligands transform its hybridization state, Eu0.4/Tb0.6; τ1 = 488.5423 μs and τ2 = 1372.6250 μs for
resulting in deviation of amino motifs from the plane of Eu0.6/Tb0.4) (Fig. S21). Furthermore, the MOF samples doped
aromatic rings. These may decrease the degree of with Eu3+ or Tb3+ emit their respective red or green color
delocalization in compound
1 and minimize the energy- excited with a standard lab UV lamp (λex = 254 nm), and those
transfer efficiency within PTD ligand, causing the quenching of samples encapsulated with different molar ratios Ln3+ ions
luminescent intensity.4 Meanwhile, the luminescent quenching display the corresponding colors, which all can be observed by
2-
of compound
1
induced by Cr2O7 anions may be ascribed to naked eye (Fig. 4d). These prominent properties may be
the interactions between framework and Cr2O72- anions.4
attributed to a large number of lanthanides and sensitizers in a
Encapsulation of Ln3+ for tunable luminescence
relatively small volume.37,
According to the above
38
advantages, the lanthanide(III) doped MOF samples can be
excellent candidates as barcod and color-tunable luminescent
materials.
The fluorescence of compound
1 and spectroscopic properties
of lanthanide cations inspire us to use compound
1 to
encapsulate lanthanide ions (Eu3+/Tb3+) for adjusting
fluorescence. Lanthanide(III) ions were introduced into the
Encapsulation of Ln3+ for white-light emission
pores of compound
1
, by which the samples were soaked in To obtain the white-light emission material based on
DMF solutions of metal nitrate salts of Eu3+ or Tb3+. The compound
1
, a more refined adjustment of the amount of Eu3+
crystalline integrity of compound
1
is not influenced by the and Tb3+ dopant is carried out. As shown in Fig. S22, we first
successful encapsulation of Ln3+, as demonstrated by PXRD reduced the Ln3+ amount from 0.5 mmol to 5*10-5 mmol with
patterns (Fig. S19). The characteristic sharp emission bands are the specific ratio of Eu3+/Tb3+ (1:4). The CIEs are showed to be
Fig. 4 The emission spectra of Tb3+ (a), Eu3+/Tb3+ (b), and Eu3+ (c) doped
1 1 illuminated with 254 nm laboratory UV light. The
. (d) The Eu3+/Tb3+-doped compound
samples were prepared by doping 50 mg MOF with 1 mmol Ln3+ in 10 mL DMF. From left to right: Tb1/Eu0, Tb0.8/Eu0.2, Tb0.6/Eu0.4, Tb0.4/Eu0.6 and Tb0/Eu1.
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Table 1. Comparisons of the quantum yields of the reported white-light emission
View Article Online
doped MOFs.
DOI: 10.1039/C9NJ02861G
Quantum
Yield[%]
Reference
number
Materials
Acf@ZnBDCA
32
39
This work
40
Eu/Tb doped compound 1
HSB-W1DCM/C6a/CBS-127
Eu/Tb@MIL-124
29
26
10
11
12
13
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60
22.8
22.4
20.4
17.4
15.2
15
41
1-Eu0.0855Gd0.6285Tb0.2860
1[Ir(ppy)2(bpy)]+
ZJU-28DSM/AF
28
42
43
NENU-524[Ir(ppy)2(bpy)]+
Eu@Al-MIL-53-COOH
NENU-521Alq3
9
44
11.4
11.3
8
45
Eu/Tb@1
42
Eu/Tb@Zn(II)-MOF
ZJU-1:1.5%Tb,2.0%Eu
Mg-CPCuI
46
6.8
5.6
4.3
3.1
2-3
47
48
10%Eu-SMOF-1
49
(Me2NH2)[RbCd4(OBA)5]·H2O
PbL2
50
51
emission was obtained by soaking compound
1 in DMF
solutions containing Eu3+ and Tb3+ in an optimal ratio of 13:7
with a total of 5*10-5 mmol (Fig. S23). The corresponding CIE
coordinate (0.3095, 0.2945) of this sample is very close to that
of the pure white light (0.3333, 0.3333) (Fig. 5b and S24).47
Moreover, the absolute quantum yield of this white-light
emission sample is 29%, which is relatively higher than those
of most reported white-light emitting doped MOFs to date
(Table 1). Considering the valuableness of rare earth salts and
the toxicity of mercury, Ln3+-doped compound
1 can be an
excellent candidate as white-light materials for its high quality
of white light emission and low concentration of Ln3+ doping.
With the aim of further exploring the potential of compound
1
, we carried out gas adsorption measurements. The porosity
is evaluated by gas adsorption of N2 at 77 K (Fig. S25). The
isotherms exhibit a sharp uptake at low-pressure region,
suggesting that the N2 molecules are preferentially adsorbed in
channels with adsorption sites. This process leads to the
distance change of each framework and increase of pore size,
resulting in the further N2 adsorption. The existence of
hysteresis loop also confirms that this compound may have
breath effect.52 The BET and Langmuir surface areas of
Fig. 5 (a) CIE chromaticity diagram for Eu3+ and Tb3+ singly doped and Eu3+/Tb3+
-
codoped compound 1. The samples were prepared by soaking 50 mg MOF into 1
mmol Ln3+ in 10 mL DMF at different molar rations Eu/Tb. 0: without Ln3+; 1: 0/1;
2: 0.2/0.8; 3: 0.4/0.6; 4: 0.6/0.4; 5: 1/0. (b) The CIE chromaticity diagram of
Eu3+/Tb3+-doped compound
1 monitored under 283 nm. The sample was
prepared by doping 50 mg as-synthesized compound
1
with 5*10-5 mmol Ln3+
(Eu3+/Tb3+, 13/7) in 10 mL DMF.
x = 0.3941, y= 0.4956; x = 0.3983, y = 0.5286; and x = 0.2966, y
= 0.3627 for 0.5 mmol Ln3+, 5*10-2 mmol Ln3+, and 5*10-5 mmol
Ln3+, respectively. The CIEs show blue shifts and gradually close
to white light area with reduction of Ln3+ concentrations. Then,
an effort was paid for optimizing the relative ratio of Eu3+ and
Tb3+ with a total of 5*10-5 mmol to obtain white-light emission.
The CIE coordinates are (0.2987, 0.3526) and (0.3026, 0.3591),
corresponding to the ratio of 1:3 and 3:7 for Eu3+/Tb3+ (Fig.
compound
mean pore width is 4.9 Å simulated by Horvath-Kawazoe mode
(Fig. S26). Inspired by the porosity of compound and the
amino-modified character of channels, the adsorption
behaviors of the activated compound for CO2 and CH4 were
then investigated. As illustrated in Fig. S27a, the CO2
1
are 449 m2 g-1 and 700 m2 g-1, respectively. The
1
1
adsorption uptake of compound
1
is 29.30 cm3 g-1 at 273 K,
which is almost 3 times as much as that of CH4 (10.26 cm3 g-1
S22). Finally, the Ln3+ doped compound
1 with white-light
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at 273 K). As prospected, it confirms that compound
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shows a
Notes and references
View Article Online
DOI: 10.1039/C9NJ02861G
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mass of free N atoms and amino groups, both of which are
conducive to the adsorption of CO2.20 This significant property
is also confirmed by the gas sorption outcomes in 298 K with
20.59 cm3 g-1 and 5.28 cm3 g-1 for CO2 and CH4, respectively.
Furthermore, the CO2 sorption capacity at 273 K is much
higher than that of MOFs previously reported.53-55 With the
data of CO2 isotherms at 273 K and 298 K and virial equation,56
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the CO2 adsorption enthalpies (Qst) of compound
1 were
computed to further comprehend the interactions between
the CO2 molecules and framework (Fig. S28). At zero loading,
the Qst value of compound 1
is 44.40 KJ mol-1 (Fig. S27b), which
is comparable to those of other complexes including amide
groups in the pores and no open metal sites.20, 54,57-59
Conclusions
In summary, a microporous MOF [Zn(OBA)2(PTD).2DMF.2H2O]n
(1
) with a 3D 3-fold interpenetrated framework has been
rationally constructed by V-shape H2OBA ligand and pre-
designed rigid PTD ligand with N-rich. Compound shows an
1
excellent thermal and chemical stability, which can maintain
its integrity of framework under 300oC or in different boiling
organic solvents. The luminescent compound
1 is capable of
2-
highly selective sensing of Cu2+ and Cr2O7 ions. The
encapsulation experiments of lanthanide(III) cations (Eu3+ and
Tb3+) confirm that the Ln3+-doped compound
1 could
potentially serve as color-tunable and barcoded luminescent
materials since they can exhibit multiband emissions and emit
different colors of light upon excitation by UV light.
Remarkably, a white-light emitting material with a relatively
high quantum yield (29%) is obtained by soaking compound
1
in 10 mL DMF solution containing 5*10-5 mmol Eu3+ and Tb3+
(13/7, Eu3+/Tb3+), which may replace the mercury-contained
fluorescent lighting. It performs a selective gas uptake for CO2
over CH4 at 273 and 298 K, revealing its potential application in
gas separation and purification. The present work provides a
reasonable and effective method for the design of
multifunctional MOF incorporated applications in chemical
probe, tunable luminescence, white-light emitting, and gas
purification.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The present work was supported by the National Natural
Science Foundation of China (21573036 and 21873018),
Foundation of the Education Department of Jilin Province
(111099108), the Fundamental Research Funds for the Central
Universities (2412019QD006), and Jilin Provincial Research
Center of Advanced Energy Materials (Northeast Normal
University).
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