Syntheses, structures, luminescence and magnetic properties of seven isomorphous metal-organic frameworks based on 2,7-bis(4-benzoic acid)-: N -(4-benzoic acid)carbazole

Article abstract of DOI:10.1039/c7nj04048b

We report herein seven novel lanthanide metal-organic frameworks (Ln-MOFs), [M(L₂₇)(DMA)(H₂O)·XH₂O]_n (TCZ-M), (M = Nd, Sm, Eu, Gd, Tb, Dy, Ho), (X = 2 or 3) (H₃L₂₇ = 2,7-bis(4-benzoic acid)-N-(4-benzoic acid)carbazole, DMA = N,N-dimethylacetamide, TCZ = "T"-shape carbazole-based MOFs, L₂₇ = fully deprotonated H₃L₂₇^3- ligand). X-ray crystallography showed that all the TCZ-M (M = Nd, Sm, Eu, Gd, Tb, Dy, Ho) are isomorphous and possess a 3,6-connected three-dimensional (3D) framework with a point symbol of {4·6²}₂{4²·6¹⁰·8³}. The photoluminescence measurement indicates that TCZ-Eu shows reddish-orange emission bands and TCZ-Sm shows both visible and near-infrared (NIR) emission bands. Magnetic susceptibility measurements show deviations from the Curie law mainly owing to the split of the ground term due to the ligand field and spin-orbit coupling in TCZ-Eu and TCZ-Sm. The magnetic properties of TCZ-M (M = Nd, Gd, Tb, Dy, Ho) are also investigated, and the results indicate a ferromagnetic interaction between the Tb³⁺ magnetic centers in TCZ-Tb and the antiferromagnetic interactions in TCZ-M (M = Nd, Gd, Dy, Ho).

Full text of DOI:10.1039/c7nj04048b

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

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Syntheses, structures, luminescence and magnetic properties of
seven isomorphous metal-organic frameworks based on 2,7-bis(4-
benzoic acid)-N-(4-benzoic acid) carbazole
Received 00th January 20xx,
Accepted 00th January 20xx
Dong-Hui Chenab, Ling Linab, Tian-Lu Shenga, Yue-Hong Wena, Xiao-Quan Zhuab, Lin-Tao Zhangab,
Sheng-Min Hua, Rui-Biao Fua and Xin-Tao Wu*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
We report herein seven novel lanthanide metal-organic frameworks (Ln-MOFs), [M(L27)(DMA)(H2O)·XH2O]n (TCZ-M), (M =
Nd, Sm, Eu, Gd, Tb, Dy, Ho), (X = 2 or 3) (H3L27 = 2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole, DMA = N,N-
3-
dimethylacetamide, TCZ = “T”-shape carbazole-based MOFs, L27 = fully deprotonated H3L27 ligand). X-ray crystallography
showed that all of the TCZ-M (M = Nd, Sm, Eu, Gd, Tb, Dy, Ho) are isomorphous and possesses a 3,6-connected three-
dimensional (3D) framework with a point symbol of {4·62}2{42·610·83}. The photoluminescence measurement indicates that
TCZ-Eu shows reddish-orange emission bands and TCZ-Sm shows both visible and near-infrared (NIR) emissions bands.
Magnetic susceptibility measurements show deviations from the Curie law mainly owing to the split of the ground term
due to the ligand field and spin–orbit coupling in TCZ-Eu and TCZ-Sm. The magnetic properties of TCZ-M (M = Nd, Gd, Tb,
Dy, Ho) are also investigated, and the results indicate a ferromagnetic interaction between Tb3+ magnetic centers in TCZ-Tb
and antiferromagnetic interactions in TCZ-M (M = Nd, Gd, Dy, Ho).
transitions originating from the 4G5/2 energy level to 6HJ (visible)
and 6FJ (NIR). The properties of Ln-MOFs could be used in
potential applications in light-emitting diodes (LEDs), biological
Introduction
Metal-organic frameworks (MOFs), assembled from organic
linkers and metal nodes, have been explored for potential
application in optical, magnetic, separation, gas sorption and
catalysis fields.1 The flexibility of organic linkers and metal
nodes provides the opportunity for engineering the properties
and structures of the MOFs.2
applications (such as immunoassay and magnetic resonance
imaging), photoluminescent sensors.4 Unique magnetic
properties are also one of the advantages of trivalent
lanthanide ions.5 Thus, Ln-MOFs based on trivalent lanthanide
ions are ideal multifunctional materials, as they are able to
incorporate with the porous properties, magnetic properties
and photoluminescent properties.6 However, the forbidden f−f
transitions of lanthanide ions exhibit a very small molar
absorption coefficient and relatively weak UV absorption with
low luminous efficiency.7 Fortunately, the aromatic
multicarboxylate compound is one of the most important
organic ligands in construction of functionalized metal-organic
frameworks.8 And it was often used as bridge ligands for
construction of luminescent Ln-MOFs. Because it has strong
absorption (conjugate with rigid structures) in the ultraviolet
region which is called “antenna effect”.9 The lanthanide metal-
The research on lanthanide metal-organic frameworks (Ln-
MOFs), usually composed of trivalent lanthanide ions and
aromatic multicarboxylate ligands, is an important branch of
the study in MOFs fields.3 Trivalent lanthanide ions have
attracted great attention due to their intense and sharp f
→f
emissions. For example, Eu3+ ion and Sm3+ ion have rich
spectroscopic properties as a result of multifold electronic
transitions. The Ln-MOFs based on Eu3+ ions usually emit red
luminescence due to the multifold electronic transitions
originating from the 5D0 energy level to FJ and the Ln-MOFs
based on Sm3+ ions emit visible and near-infrared (NIR)
emissions sometimes which due to the multifold electronic
7
organic
frameworks,
assembled
with
aromatic
multicarboxylate ligands, may perform excellent “antenna
effect”.10 Therefore, with excellent structural diversity and
amazing physical properties related to unique 4f-electrons, Ln-
MOFs occupy a special position among MOFs. Recently, there
are some works about Ln-MOFs has been reported already
according to these phenomena.11
Considering all of the above-mentioned, 2,7-bis(4-benzoic
acid)-N-(4-benzoic acid) carbazole
(H3L27), a conjugated
tricarboxylic acid ligand, was employed as an organic linker.
And its reaction with the nitrates of trivalent lanthanide ions
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was predicted to form novel functional Ln-MOFs. Herein, we HORIBA Jobin Yvon Ultima2 Inductively Coupled Plasma OES
present seven three-dimensional Ln-MOFs, spectrometer (ICP). Magnetic susceptibilities of crystalline
L27)(DMA)(H2O)· H2O]n (TCZ-M), ( = Nd, Sm, Eu, Gd, Tb, samples were measured with a Quantum Design MPMS-XL
Dy, Ho), ( = 2 or 3) (DMA = N,N-dimethylacetamide, TCZ = SQUID susceptometer under an applied magnetic field of 1
[M
(
X
M
X
“T”-shape carbazole-based MOFs), which exhibit good kOe in the 2–300 K range. Diamagnetic corrections were made
using Pascal's constants.12
luminescent and magnetic properties, respectively.
Synthesize of 2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole
(H3L27):
Experimental
The synthesis in this work start from commercially available
4,4’-dibromobiphenyl. H3L27 was synthesized according to the
literature procedure and the synthetic method is shown in
Supporting Information. (Scheme S1) 13
Materials and Methods
Potassium tert-butoxide, 4,4’-dibromobiphenyl, ethyl 4-
fluorobenzoate, potassium carbonate, tetrakis(triphenylphosp-
hine)palladium(0),
Nd(NO3)3·6H2O,
Sm(NO3)3·6H2O,
Eu(NO3)3·6H2O, Gd(NO3)3·6H2O, Tb(NO3)3·6H2O, Dy(NO3)3·6H2O,
Ho(NO3)3·6H2O and solvents were purchased commercially and
used directly. Elemental analyses (C, H and N) were performed
with an Elementar Vario EL-Cube Element Analyzer. Powder X-
ray diffraction (PXRD) data were collected on a Rigaku MiniFlex
600 diffractometer using Cu Kα radiation (λ = 0.154 nm).
Infrared spectra were recorded with KBr pellets in the range
Synthesis of [Nd(L27)(DMA)(H2O)·3H2O]n (TCZ-Nd)
Solvothermal reaction of Nd(NO3)3
·6H2O (21.9 mg, 0.05 mmol),
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
)
(26.3 mg, 0.05 mmol) in the mixture of N,N’-
dimethylacetamine (DMA) (2 ml) and H2O (0.5 ml) at 348 K for
4 days gave rise to lavender prism crystals of TCZ-Nd (19.3 mg,
Yield: 48.8%). Anal. Calcd (%) for C37H35N2O11Nd: C 53.67, H
4.26, N 3.38. Found: C 53.66, H 4.26, N 3.38.
4000-400cm-1 on
spectrometer. Thermogravimetric analysis (TGA) experiments
were carried out on NETZSCH STA 449C Jupiter
a Perkin-Elmer Spectrum One FT-IR
a
Synthesis of [Sm(L27)(DMA)(H2O)·3H2O]n (TCZ-Sm)
thermogravimetric analyzer in flowing nitrogen with the
sample heated in an Al2O3 crucible from room temperature to
Solvothermal reaction of Sm(NO3)3
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
(26.3 mg, 0.05 mmol) and 69% concentrated nitric acid (10 L),
·6H2O (22.2 mg, 0.05 mmol),
)
1000 oC at a heating rate of 10 K min−1. Metal elemental
·
μ
analyses (for lanthanide metal ions) were performed with a
Compound
TCZꢀNd
TCZꢀSm
TCZꢀEu
TCZꢀGd
Empirical formula
C37H35N2O11Nd
C37H33N2O10Sm
C37H33N2O10Eu
C37H33N2O10Gd
Formula weight
Crystal system
Space group
a(Å)
827.91
Monoclinic
P21/c
816.00
Monoclinic
P21/c
817.60
Monoclinic
P21/c
822.90
Monoclinic
P21/c
15.986(7)
8.403(3)
28.487(13)
90
15.793(7)
8.363(3)
28.515(12)
90
15.776(3)
8.3587(16)
28.529(5)
90
15.696(4)
8.307(2)
28.470(8)
90
b(Å)
c(Å)
α(°)
β(°)
96.253(5)
90
96.516(7)
90
96.501(4)
90
96.418(5)
90
γ(°)
V(Å3)
3804(3)
4
3742(3)
4
3737.9(12)
4
3689.0(17)
4
Z
Temperature(K)
D(Mg mꢀ3)
ꢀ(mmꢀ1)
F(000)
293(2)
293(2)
293(2)
293(2)
1.445
1.448
1.453
1.517
1.414
1.619
1.727
1.848
1676
1644
1648
1652
a
R1 ,wR2b(I>2σ(I))
0.0879,0.1979
2.53 to 27.51
ꢀ20≤ h ≤ꢀ20
ꢀ10≤ k ≤8
ꢀ36≤ l ≤36
1.169
0.0770,0.1846
2.59 to 27.46
ꢀ20≤ h ≤20
ꢀ10≤ k ≤10
ꢀ36≤ k ≤33
1.125
0.0530,0.1253
2.54 to 27.52
ꢀ20≤ h ≤20
ꢀ10 ≤ k ≤10
ꢀ36≤ k ≤35
1.108
0.0496, 0.1199
2.55 to 27.49
ꢀ17≤ h ≤20
ꢀ10≤ k ≤10
ꢀ36≤ k ≤36
1.133
θranges(deg)
h,k,l ranges
GOF on F2
a R = ∑||FO| ꢀ FC||/∑|F0|. b wR2 = [P[w(FO2 ꢀ FC2)2]/∑[(F02)2]]1/2
.
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Table 2 Crystal and X-ray experimental data for compounds TCZ-Tb, TCZ-Dy, TCZ-Ho.
Compound
TCZꢀTb
TCZꢀDy
TCZꢀHo
Empirical formula
Formula weight
Crystal system
Space group
a(Å)
C37H33N2O10Tb
824.57
C37H33N2O10Dy
828.15
C37H35N2O11Ho
848.60
Monoclinic
P21/c
Monoclinic
P21/c
Monoclinic
P21/c
15.729(4)
8.3089(18)
28.483(7)
90
15.735(7)
8.290(3)
28.436(12)
90
15.682(5)
8.316(3)
28.526(11)
90
b(Å)
c(Å)
α(°)
β(°)
96.448(4)
90
96.414(8)
90
96.325(9)
90
γ(°)
V(Å3)
3699.1(14)
4
3686(3)
4
3697(2)
4
Z
Temperature(K)
D(Mg mꢀ3)
ꢀ(mmꢀ1)
F(000)
293(2)
293(2)
293(2)
1.481
1.492
1.524
1.962
2.077
2.19
1656
1660
1704
a
R1 ,wR2b(I>2σ(I))
0.0573,0.1373
2.55 to 27.51
ꢀ20≤ h ≤20
ꢀ10≤ k ≤10
ꢀ35≤ l ≤36
1.119
0.0511,0.1250
2.56 to 27.47
ꢀ20≤ h ≤20
ꢀ10≤ k ≤10
ꢀ36≤ l ≤36
1.094
0.0842,0.1685
2.55 to 27.50
ꢀ17≤ h ≤20
ꢀ10≤ k ≤10
ꢀ36≤ l ≤36
1.183
θranges(deg)
h,k,l ranges
GOF on F2
a R = ∑||FO| ꢀ FC||/∑|F0|. b wR2 = [P[w(FO2 ꢀ FC2)2]/∑[(F02)2]]1/2
.
which is used for regulating the pH value, in the mixture of Yield: 51.0%). Anal. Calcd (%) for C37H33N2O10Gd: C 54.00, H
DMA (2 ml) and H2O (0.5 ml) at 348 K for 4 days gave rise to 4.04, N 3.40. Found: C 54.06, H 4.05, N 3.39.
lavender prism crystals of TCZ-Sm (17.8 mg, Yield: 44.9%). Anal.
Synthesis of [Tb(L27)(DMA)(H2O)·2H2O]n (TCZ-Tb)
Calcd (%) for C37H35N2O11Sm: C 53.28, H 4.23, N 3.36. Found: C
53.28, H 4.25, N 3.35.
Solvothermal reaction of Td(NO3)3
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
(26.3 mg, 0.05 mmol) and 69% concentrated nitric acid (20 L)
·6H2O (22.6 mg, 0.05 mmol),
)
Synthesis of [Eu(L27)(DMA)(H2O)·2H2O]n (TCZ-Eu)
μ
Solvothermal reaction of Eu(NO3)3
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
(26.3 mg, 0.05 mmol) and 69% concentrated nitric acid (10 L) Yield: 50.6%). Anal. Calcd (%) for C37H33N2O10Tb: C 53.89, H
·
6H2O (22.3 mg, 0.05 mmol), in the mixture of DMA (2 ml) and H2O (0.5 ml) at 348 K for 4
)
days gave rise to lavender prism crystals of TCZ-Tb (20.4 mg,
μ
in the mixture of DMA (2 ml) and H2O (0.5 ml) at 348 K for 4 4.03, N 3.40. Found: C 53.90, H 4.02, N 3.40.
days gave rise to lavender prism crystals of TCZ-Eu (24.3 mg,
Synthesis of [Dy(L27)(DMA)(H2O)·2H2O]n (TCZ-Dy)
Yield: 60.9%). Anal. Calcd (%) for C37H33N2O10Eu: C 54.35, H
4.07, N 3.42. Found: C 54.36, H 4.06, N 3.41.
Solvothermal reaction of Dy(NO3)3
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
(26.3 mg, 0.05 mmol) and 69% concentrated nitric acid (20 L)
·6H2O (22.8 mg, 0.05 mmol),
)
Synthesis of [Gd(L27)(DMA)(H2O)·2H2O]n (TCZ-Gd)
μ
Solvothermal reaction of Gd(NO3)3
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
(26.3 mg, 0.05 mmol) and 69% concentrated nitric acid (20 L) Yield: 54.5%). Anal. Calcd (%) for C37H33N2O10Dy: C 53.66, H
·
6H2O (22.5 mg, 0.05 mmol), in the mixture of DMA (2 ml) and H2O (0.5 ml) at 348 K for 4
)
days gave rise to lavender prism crystals of TCZ-Dy (22.1 mg,
μ
in the mixture of DMA (2 ml) and H2O (0.5 ml) at 348 K for 4 4.01, N 3.38. Found: C 54.36, H 4.06, N 3.38.
days gave rise to lavender prism crystals of TCZ-Gd (20.6 mg,
Synthesis of [Ho(L27)(DMA)(H2O)·3H2O]n (TCZ-Ho)
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analysis (TGA).16 Crystal data for TCZ-M
Tb, Dy, Ho) are presented in Table 1 and Table 2. Selected
bond lengths and angles of TCZ-M = Nd, Sm, Eu, Gd, Tb, Dy,
(M = Nd, Sm, Eu, Gd,
(
M
Ho) are listed in Table S1 of Supporting Information.
Photophysical measurements
The solid-state luminescence emission/excitation spectra and
solid-state luminescence lifetimes were recorded on an
Edingburgh
Insruments
FLS980
fluorescence
spectrophotometer. The quantum yields of the solid-state
samples were determined by an absolute method using an
integrating sphere on an Edingburgh Insruments FLS920
spectrometer. The lifetimes of the solid-state samples were
acquired on an Edinburgh Analytical FLS920 instrument with a
Picoseconds Laser Diode.
Results and discussion
Fig.1 (a) Secondary building units (SBUs) of TCZ-M (M = Nd, Sm, Eu, Gd, Tb, Dy,
Crystal structure of TCZ-M (M = Nd, Sm, Eu, Gd, Tb, Dy, Ho)
Ho); (b) The coordination environment of deprotonated L27 ligand molecule;
(c) View of the 3D frameworks in TCZ-M(M=Nd, Sm, Eu, Gd, Tb, Dy, Ho).
Structural analysis according to single crystal X-ray diffraction
indicates TCZ-M
isomorphous, crystallize in the monoclinic
As shown in Fig.1 TCZ-M = Nd, Sm, Eu, Gd, Tb, Dy, Ho)
(
M
= Nd, Sm, Eu, Gd, Tb, Dy, Ho) are
P
21/ space group.
c
Solvothermal reaction of Ho(NO3)3
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
(26.3 mg, 0.05 mmol) and 69% concentrated nitric acid (30 L)
·6H2O (22.8 mg, 0.05 mmol),
,
(M
)
exhibit 3D frameworks and the asymmetric unit includes a fully
deprotonated L27 ligand, a respective lanthanide metal cation,
a coordinated DMA molecule, a coordinated H2O molecule and
two or three free H2O molecules. Each lanthanide metal cation
is eight coordinated by four O atoms from two carboxyl groups
of L27 ligands, an O atom from a DMA molecule, an O atom
from a H2O molecule and two O atoms from two carboxyl
groups which are the bridge between two lanthanide metal
cations.
μ
in the mixture of DMA (2 ml) and H2O (0.5 ml) at 348 K for 4
days gave rise to lavender prism crystals of TCZ-Ho (21.4 mg,
Yield: 52.7%). Anal. Calcd (%) for C37H35N2O11Ho: C 52.37, H
4.16, N 3.30. Found: C 52.38, H 4.14, N 3.31.
Single-Crystal Structure Determination.
The X-ray single-crystal structure analyses for the TCZ-M
Nd, Sm, Eu, Gd, Tb, Dy, Ho) were collected on a Rigaku Saturn
724HG CCD diffractometer (Mo Kα radiation = 0.71073Å
(M =
Topologically, the L27 ligand could be regard as 3-connected
node and two lanthanide metal cations bridged by two
carboxyl groups of L27 ligands could be simplified as a 6-
λ
graphite-monochromator) at 293(2) K. All of the structure
were solved by direct methods and refined by full matrix least-
squares of F2 using the SHELXL-2018/1 program.14 Hydrogen
atoms were added in idealized positions. The SQUEEZE routine
of the PLATON software suite was used in removing highly
disordered solvent molecules.15 The final formulas were
calculated according to the Squeeze results combined with the
results from elemental analyses and thermogravimetric
connected node. As shown in Fig.2, the structure of TCZ-M
(M
= Nd, Sm, Eu, Gd, Tb, Dy, Ho) can be described as a rtl rutile 3,
6-connected network with
{4·62}2{42·610·83}.17
a
Schläfli symbol of
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Fig. 4 Solid-state emission spectra of TCZ-Sm.
X-ray powder diffraction and thermal analysis
Fig. 5 Solid-state emission spectra of TCZ-M (M = Nd, Gd, Tb, Dy, Ho).
Powder X-ray diffraction (PXRD) for the bulk samples of TCZ-M
= Nd, Sm, Eu, Gd, Tb, Dy, Ho) were carried out at room
temperature. The experimental PXRD patterns also proves that
TCZ-M = Nd, Sm, Eu, Gd, Tb, Dy, Ho) are isomorphous
(M
1, 2, 3, 4) transitions of Eu3+ ions. The most intense emission
5
peak at 618 nm is due to the electric dipole induced D0
→
7F2
(
M
structures and all of them correspond well with the simulated
from the data of single crystal X-ray diffraction and are shown
in Fig. S2 and Fig. S3. To estimate the thermal stability,
thermogravimetric analysis (TGA) experiments were
transition, which is highly sensitive to the coordination
environment of Eu3+ ions. With lower site symmetry of Eu3+
ions, the intensity of the emission peak at 618 nm increase
obviously. The second intense emission at 594 nm corresponds
to the magnetic dipole induce 5D0 7F1 transition, which is
→
performed on polycrystalline samples of TCZ-M (M = Nd, Sm,
fairly insensitive to the environment of the Eu3+ ions.19
The Sm3+ ion in TCZ-Sm has rich spectroscopic properties as
a result of multifold electronic transitions originating from the
Eu, Gd, Tb, Dy, Ho) under a N2 atmosphere with a heating rate
of 10 oC
·
min-1 in the range of 30 - 800 oC. From room
o
temperature to 170 C, a weight loss of 3 – 5 % is ascribed to
the loss of the free solvent molecules between the crystals.
From 175 to 275 oC, free solvent molecules and coordinated
DMA molecules were removed generally with a weight loss of
19 - 22%. The frame work collapses and decomposes after 540
4G5/2 energy level to 6HJ (
and 6FJ (
= 1/2, 3/2, 5/2, 7/2, 9/2, 11/2). Both visible and near-
J = 5/2, 7/2, 9/2, 11/2, 13/2, 15/2)
J
infrared (NIR) luminescence could be produced by the
multifold electronic transitions. So far, Sm3+-based emitting
compounds are rather limited and even less are concerned
about their near-infrared emissions. Upon excitation at 370
nm at room temperature, the solid sample of TCZ-Sm displays
multiple emission peaks at 427 (ligand), 562 (6H5/2), 598 (6H7/2),
644 (6H9/2), 704 (6H11/2), 786 (6H13/2), 872 (6F1/2), 896 (6F3/2), 914
(6H13/2), 940 (6F5/2), 1020 (6F7/2), 1162 (6F9/2), 1287 (6F11/2) nm
oC. (Fig. S4
)
Photoluminescence properties
The photoluminescence properties of TCZ-M (M = Nd, Sm, Eu,
Gd, Tb, Dy, Ho) and H3L27 ligand were investigated under room
temperature. The photophysical data are summarized in Table
3
.The free solid-state H3L27 ligand show a blue fluorescent
emission band at 459 nm under 375 nm wavelength excitation
with decay lifetime τH L27 = 3.78 ns, which is probably due to
(
Fig. 4). The nature of these emissions can be confirmed by the
measurement of their decay. The broad band centered at 427
nm is attributable to the emission of the L27 ligand with a
decay lifetime 2.22 ns, which is probably due to π* → n or π*
→ π transitions. The remaining five narrow peaks (562, 598,
644, 699, 808 nm) has decay lifetimes approximately 4.0 ꢁs,
which are correlated with the transitions from G5/2 to H5/2
6H7/2, 6H9/2, 6H11/2, 6H13/2, respectively.20
π
*
3
→
π
transitions.18 Under excitation at 399 nm, the solid-state
emission spectrum of TCZ-Eu was observed with sharp and
well resolved emission peak (Fig. 3). TCZ-Eu displays emission
4
6
bands at 580, 592, 617, 652, 699 nm in the visible region with
5
decay lifetimes about 470 ꢁs, coming from the D0
,
→ J = 0,
7FJ (
H3L27
TCZꢀNd
TCZꢀSm
TCZꢀEu
TCZꢀGd
TCZꢀTb
TCZꢀDy
TCZꢀHo
427, 562, 598, 644, 704, 786,
872, 896, 914, 940, 1020,
1162, 1287
580, 592, 617,
652, 699
λem(nm)
459
426
430
429
429
413
τ (ns)
3.78
1.63
2.11
2.22 and 4×103
4.7×105
15.46
1.15
7.86
1.27
6.63
1.10
6.25
0.83
Φ (%)
14.26
0.92 (in visible light range)
< 0.5
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Fig. 6 Plots of χM (black), χMT and χM-1 vs. T for TCZ-Nd (a), TCZ-Gd (b), TCZ-Tb(c), TCZ-Dy(d), TCZ-Ho(e).
As shown in Fig.5, the solid-state emission spectra of TCZ-M in Ln-MOFs is much less pronounced than in the 3d ions in
= Nd, Gd, Tb, Dy) display intense emission bands centered most of MOFs.22
at 426, 430, 429, 429 nm respectively under excitation at 370 As shown in Fig. 6a, the χMT value at room temperature for
nm. The blue shifts of TCZ-M
= Nd, Gd, Tb, Dy) are TCZ-Nd is 2.96 cm3·K mol-1 and the value is close to the
tentatively assigned strong electrostatic interaction between expected values of 3.28 cm3·K·mol-1 for two uncoupled Nd3+
the L27 ligands and metal ions by donation of the lone pair ions (gNd = 8/11, = 9/2). The temperature dependence of the
electrons of O atoms to the empty orbitals of the metal ions. reciprocal molar susceptibility above 50 K follows the Curie-
13,18a,18d,21The crystals of TCZ-Ho exhibit the blue emission with Weiss law with = 3.18 cm3·K·mol–1,
= –48.03 K. The
(M
(
M
S
C
θ
an emission maximum at 413 nm and the blue shift may due to relatively big negative Weiss constant indicates dominating
the absorption of the Ho3+ ions in TCZ-Ho. (Fig.5) The emission antiferromagnetic interactions between Nd3+ ions.
decay lifetimes of TCZ-M
(
M
= Nd, Gd, Tb, Dy, Ho) were found
The χMT value of TCZ-Gd at 300 K is 14.00 cm3·K·mol–1,
to be τTCZ-Nd = 1.626 ns, τTCZ-Gd = 1.147 ns, τTCZ-Tb = 1.274 ns, τTCZ- which is slightly lower than the expected value (15.59
cm3·K·mol–1) of two isolated spin-only Gd3+ ions (gGd = 1.99,
S =
Dy = 1.103 ns and τTCZ-Ho = 0.829 ns.
7/2). The χMT value of TCZ-Gd keeps steadily from room
Magnetic properties
temperature to 18 K with decreasing temperature. Upon
The magnetic properties were measured using a crystalline cooling, the χMT value of TCZ-Gd rapidly decreased to a value
sample, whose phase purity was confirmed by powder X-ray of 13.30 cm3·K·mol-1. The magnetic behavior in the
diffraction.
The
temperature-dependent
magnetic temperature range of 2-300 K follows the Curie–Weiss Law
susceptibility of TCZ-M
(
M
= Nd, Sm, Eu, Gd, Tb, Dy, Ho) was with C = 14.00 cm3·K·mol–1 and Weiss constant θ = -0.398 K
investigated in the range of 2 – 300 K at a direct current field
of 1.0 kOe.
Magnetic studies that this series of Ln-MOFs shows different
magnetic properties. The results are illustrated in Fig. 6 as
plots of χMT and χM versus T, where χM is the molar magnetic
susceptibility.
The magnetic properties of lanthanide (III) ions are
obviously different from those of 3d ions. The 4f orbitals are
shielded by the fully occupied 5s and 5p orbitals and the
unfilled magnetic shell of electrons (the 4f shell) imbedded in
the interior of the ion. The 4fn electrons are almost not
involved in the bonds between the lanthanide (III) ion and its
nearest neighbors. This makes the energy states of the 4fn
configurations approximate to the energy states of the free
ions in a first approximation. The influence of the environment
6 | J. Name., 2012, 00, 1-3
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ꢄ
which indicates that there is weak antiferromagnetic coupling
between the adjacent Gd3+ ions. Theoretically, Gd3+ ions with
4f7 configuration are very stable in terms of the surrounding
ꢂꢃ
ꢉ
χꢀ ꢁ ꢅꢆꢇꢈ ꢊ
(1)
8
With ꢋ ꢁ ꢌ2.143x ꢍ 7.347ꢎ ꢍ ꢌ42.92x ꢍ 1.641ꢎꢏꢐꢑꢒ ꢍ
environment. Its ground state is the S7/2, there is no spin–
ꢄ
orbit coupling since
above the ground state, the crystal field has no noticeable
23
L
= 0, the first excited state is 30000 cm-1
ꢐꢄꢑꢒ
ꢌ283.7x ꢓ 0.6571ꢎꢏꢐꢔꢈ ꢍ ꢌ620.6x ꢓ 1.94ꢎꢏ
ꢍ ꢌ1122x ꢓ
ꢄ
effect on its magnetic properties. (Fig. 6b
)
2.835ꢎꢏꢐꢕꢖꢈ ꢍ ꢌ1813x ꢓ 3.556ꢎꢏꢐꢗꢗꢈ/ꢕ; ꢘ ꢁ 3 ꢍ 4ꢏꢐꢙꢈ/ꢕ
5ꢏꢐꢔꢈ ꢍ 6ꢏꢐꢕꢙꢈ/ꢕ ꢍ 7ꢏꢐꢕꢖꢈ ꢍ 8ꢏꢐꢗꢗꢈ/ꢕ; x ꢁ ꢚ/ꢛꢜ.
ꢍ
For TCZ-Tb, the room temperature χMT value is 21.39
cm3·K·mol–1, which is close to the theoretical value of 23.6
cm3·K·mol–1 for two Tb3+ ions (gTb = 3/2,
S = 6). Upon cooling,
And
magneton,
temperature.
As shown in Fig.7, the best fit value for the spin-orbit
coupling parameter is
= 196 cm-1. Values around 200 cm-1 are
N
stands for Avogadro’s number;
β
stands for Bohr
the value increases gradually to reach a maximum of 21.81
cm3·K·mol–1 at 64 K. And then decreases to 14.17 cm3·K·mol–1
at 2 K. The magnetic behavior in the temperature range of 2-
k
stands for Boltzmann constant,
T
stands for
300 K follows the Curie–Weiss Law with
and Weiss constant 0.077 K. And there is weak
ferromagnetic coupling between the Tb3+ ions at higher
temperature. (Fig. 6c
C
= 21.45 cm3·K·mol–1
λ
θ
=
considered as expected and the magnetic susceptibility plot
reproduced the theoretical values till 100 K. Below 100 K the
experimental magnetic susceptibility values lie below the
theoretical ones, which suggest some weak antiferromagnetic
couplings amongst the Sm3+ ions.23b
)
As shown in Fig. 6d, the χMT value at room temperature for
TCZ-Dy is 28.33 cm3·K·mol–1 and the value is in agreement with
the expected values of 26.77 cm3·K·mol–1 for two uncoupled
Similar to Sm3+, the ground term (7F) of Eu3+ is split into six
Dy3+ ions (gDy = 4/3,
Curie–Weiss law over the whole temperature range and
resulted in = –3.17 K. The negative θ
= 26.96 cm3·K·mol–1,
S = 15/2). The χΜ of TCZ-Dy obeys the
7FJ levels by the spin-orbit coupling,
λ, with J ranging from 0 to
6. The value of is small enough for the first excited state to
λ
be thermally polulated (about 300 cm-1). It also causes the
deviation of the magnetic susceptibility plot from the Curie law.
The magnetic susceptibility of Eu3+ in TCZ-Eu follows the
C
θ
value of TCZ-Dy indicates the dominance of antiferromagnetic
interactions between the Dy3+ ions.
The χMT value of TCZ-Ho at 300 K is 28.14 cm3·K·mol–1,
which is very close to the expected value (28.12 cm3·K·mol–1)
numerical expression given in eqn (2) 19
:
ꢄ
ꢂꢃ
ꢝ
of two isolated spin-only Ho3+ ions (gHo = 5/4,
the curves of χM-1 vs
28.19 cm3·K·mol–1,
weak antiferromagnetic coupling between adjacent Ho3+ ions.
Fig. 6e
The ground term (6H) for Sm3+ ions is close in energy to the
S
= 8). Moreover,
in 2-300 K obey the Curie-Weiss law (
= –2.58 K), indicating the occurrence of
χꢀ ꢁ ꢅꢆꢇꢈ ꢞ
(2)
T
C =
θ
With C ꢁ 24 ꢍ ꢟꢕꢙꢈ ꢓ ꢕꢅꢠꢏꢐꢈ ꢍ ꢟꢡꢅꢗꢈ ꢓ ꢗꢕꢠ ꢏꢐꢅꢈ ꢍ ꢟ189x ꢓ
ꢕ
ꢕ
ꢙꢕꢠ ꢏꢐꢢꢈ ꢍ ꢟ405x ꢓ ꢣꢕꢠꢏꢐꢡꢖꢈ ꢍ ꢟꢡꢤꢔꢗꢈ ꢓ ꢡꢕꢡꢠꢏꢐꢡꢗꢈ ꢍ ꢌꢕꢤꢗꢙꢈ ꢓ
(
)
ꢕ
ꢕ
13/2ꢎꢏꢐꢕꢡꢈ; D ꢁ 1 ꢍ 3ꢏꢐꢈ ꢍ 5ꢏꢐꢅꢈ ꢍ 7ꢏꢐꢢꢈ ꢍ 9ꢏꢐꢡꢖꢈ
ꢍ
first excited state and it can be thermally populated at room
temperature and above, this causes the deviation of the
11ꢏꢐꢡꢗꢈ ꢍ 13ꢏꢐꢕꢡꢈ; x ꢁ ꢚ/ꢛꢜ.
magnetic susceptibility plot from the Curie law. Since
λ is small
enough for the first excited state to be thermally populated
Best fit of the magnetic susceptibility data to eqn (2) in the
= 358 cm-1. Value
(around 200 cm-1), the magnetic susceptibility follows the temperature range 130 – 300 K gives
λ
numerical expression given in eqn (1) 23
around 300 cm-1 are considered in the expected range and the
magnetic susceptibility plot reproduces the theoretical values
till 130 K. (Fig. 8) The deviation observed below 130 K can be
due to weak ferromagnetic interactions between the Eu3+
ions.19b
Conclusions
In summary, we have successfully prepared seven new Ln-
MOFs, TCZ-M (M = Nd, Sm, Eu, Gd, Tb, Dy, Ho), with 2,7-bis(4-
benzoic acid)-N-(4-benzoic acid) carbazole. All of the seven Ln-
MOFs are isomorphous and the structure could be described
as a rtl rutile 3, 6-connected network with a Schläfli symbol of
{4·62}2{42·610·83}. The strong photoluminescence of TCZ-Eu
indicates it may be good potential candidates for red
luminescent materials. For TCZ-Sm
luminescence both in visible and near-infrared region. And
other Ln-MOFs, TCZ-M = Nd, Gd, Tb, Dy, Ho), also display
, it shows sensitized
(
M
strong emissions in the visible region, which are similar to the
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Stanley, B. J. Holliday, Coord. Chem. Rev., 2012, 256, 1520;
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emission of the ligands. And the seven isomorphous MOFs
with different luminescent properties indicates that they may
be good potential candidates for luminescent materials by
doping the lanthanide metal ions. The magnetic properties of
TCZ-M (M = Nd, Sm, Eu, Gd, Tb, Dy, Ho) are very different,
5
6
though the magnetic centers are mediated through the same
carboxylate bridge. The Tb3+ ions in TCZ-Tb exhibit weak
ferromagnetic coupling between the adjacent Tb3+, while weak
antiferromagnetic coupling between adjacent ions occurs in
TCZ-M (M
= Nd, Gd, Dy, Ho). The Eu3+ in TCZ-Eu and the Sm3+
in TCZ-Sm is governed by the spin–orbit coupling and the
deviations from the theoretical expression being as well due to
the splitting of the ground term at low temperatures together
with some magnetic interaction.
7
8
Acknowledgements
The authors gratefully acknowledge financial support from the
National Natural Science Foundation of China (21233009 and
21203194), the 973 program (2014CB845603), the Strategic
Priority Research Program of the Chinese Academy of Sciences
9
H. Ji, X. Li, D. Xu, Y. Zhou, L. Zhang, Z. Zuhra and S. Yang,
Inorg. Chem., 2017, 56, 156.
，Grant No. XDB20000000.
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Zhou, F. K. Zheng, G. C. Guo, J. Am. Chem. Soc., 2009, 131,
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Nenoff, J. Am. Chem. Soc., 2012, 134, 3983.
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M. A. AlDamen and M. L. Tong, Dalton Trans., 2017, 46,116.
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Li and X. Wu, CrystEngComm, 2017, 19, 2632.
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Graphical Abstract
Seven isomorphous lanthanide metal-organic frameworks with special luminescence and
magnetic properties are synthesized and characterized.