Lanthanide coordination polymers based on 5-(2′-carboxylphenyl) nicotinate: Syntheses, structure diversity, dehydration/hydration, luminescence and magnetic properties

Article abstract of DOI:10.1039/c2dt32674d

Twelve lanthanide coordination polymers associated with the organic ligand 5-(2′-carboxylphenyl) nicotinic acid (H₂cpna): {[Ln(Hcpna)(cpna)(phen)]·H₂O}_n (Ln = Sm (1), Tb (2), Ho (3), phen = 1,10-phenanthroline), {[Sm(Hcpna)(cpna)(phen)] ·2H₂O}_n (4), {[Ln₂(cpna) ₃(H₂O)₃]·4H₂O}_n (Ln = Y (5), Tb(6), Dy (7), Ho (8)), [Lu₂(cpna)₃(H ₂O)₂]_n (9), {[Y₂(cpna) ₃(phen)₂(H₂O)]·H₂O} _n (10), and [Ln(cpna)(phen)(NO₃)]_n (Ln = Tm (11), Lu (12)) have been prepared by hydrothermal methods and structurally characterized. The structure analyses reveal that complexes 1-3 are isostructural and possess unique three-dimensional (3D) frameworks based on the dodecanuclear Sm/Tb/Ho macrocycles. Complex 4 exhibits a one-dimensional (1D) wheel-chain structure, which further builds three-dimensional (3D) supramolecular architecture via O-H...N hydrogen-bonding interactions. Complexes 5-8 are also isostructural and display three-dimensional (3D) open frameworks, which possess two types of channels along the a- and b-axis, respectively. Complexes 9 and 10 feature three-dimensional (3D) frameworks and are created from tetranuclear and dinuclear units, respectively. Complexes 11 and 12 are isostructural and demonstrate one-dimensional (1D) double chain structures, which further build three-dimensional (3D) supramolecular architecture via C-H...O hydrogen-bonding. The results show that the pH value of the reaction system, anion, auxiliary ligand and lanthanide contraction play a significant role in determining the structures of the complexes. In addition, the results of luminescent measurements for compounds 2 and 6 in the solid state at room temperature indicate that the different types of structures have a dissimilar influence on their characteristic luminescence. The magnetic properties of compounds 1, 3, 4, 7 and 11 have been investigated. Furthermore, thermal stabilities for 1-12 and the dehydration/hydration properties of compound 6 have also been studied.

Full text of DOI:10.1039/c2dt32674d

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Lanthanide coordination polymers based on
5-(2’-carboxylphenyl) nicotinate: syntheses, structure
diversity, dehydration/hydration, luminescence and
magnetic properties†
Cite this: Dalton Trans., 2013, 42, 4822
Jin-Zhong Gu,* Jiang Wu, Dong-Yu Lv, Yu Tang, Kongyang Zhu and Jincai Wu
Twelve lanthanide coordination polymers associated with the organic ligand 5-(2’-carboxylphenyl) nic-
otinic acid (H2cpna): {[Ln(Hcpna)(cpna)(phen)]·H2O}n (Ln = Sm (1), Tb (2), Ho (3), phen = 1,10-phen-
anthroline), {[Sm(Hcpna)(cpna)(phen)]·2H2O}n (4), {[Ln2(cpna)3(H2O)3]·4H2O}n (Ln = Y (5), Tb(6), Dy (7),
Ho (8)), [Lu2(cpna)3(H2O)2]n (9), {[Y2(cpna)3(phen)2(H2O)]·H2O}n (10), and [Ln(cpna)(phen)(NO3)]n (Ln =
Tm (11), Lu (12)) have been prepared by hydrothermal methods and structurally characterized. The
structure analyses reveal that complexes 1–3 are isostructural and possess unique three-dimensional (3D)
frameworks based on the dodecanuclear Sm/Tb/Ho macrocycles. Complex 4 exhibits a one-dimensional
(1D) wheel-chain structure, which further builds three-dimensional (3D) supramolecular architecture via
O–H⋯N hydrogen-bonding interactions. Complexes 5–8 are also isostructural and display three-
dimensional (3D) open frameworks, which possess two types of channels along the a- and b-axis, respect-
ively. Complexes 9 and 10 feature three-dimensional (3D) frameworks and are created from tetranuclear
and dinuclear units, respectively. Complexes 11 and 12 are isostructural and demonstrate one-dimen-
sional (1D) double chain structures, which further build three-dimensional (3D) supramolecular architec-
ture via C–H⋯O hydrogen-bonding. The results show that the pH value of the reaction system, anion,
auxiliary ligand and lanthanide contraction play a significant role in determining the structures of the
complexes. In addition, the results of luminescent measurements for compounds 2 and 6 in the solid
state at room temperature indicate that the different types of structures have a dissimilar influence on
their characteristic luminescence. The magnetic properties of compounds 1, 3, 4, 7 and 11 have been
investigated. Furthermore, thermal stabilities for 1–12 and the dehydration/hydration properties of
compound 6 have also been studied.
Received 9th November 2012,
Accepted 4th January 2013
DOI: 10.1039/c2dt32674d
www.rsc.org/dalton
transition metal ions, lanthanide ions have higher coordi-
nation numbers and more flexible coordination geometries,
Introduction
Recently, the preparation of lanthanide coordination polymers which make it even more difficult to control the structures.
has provoked considerable current interest owing to their enor- Thus, it is a great challenge to control structures with desired
mous variety of intriguing structural topologies as well as great properties because many factors affect the result, such as the
potential applications in the area of catalysis, gas storage, sep- coordination geometry of the central metal ions, connection
aration, magnetism and luminescence.1 In comparison with modes of organic ligands, reaction temperature, the ratio of
reagents, solvents, pH value, anions, and so on.2 Investigations
on how these factors affect the final structures will help us
State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous
understand which reaction conditions afford lanthanide
Metal Chemistry and Resources Utilization of Gansu Province and College of
coordination polymers with expected structures. Recently, we
Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000,
have been interested in the coordination chemistry of 5-(2′-car-
P. R. China. E-mail: gujzh@lzu.edu.cn; Fax: +86-931-89151962;
boxylphenyl) nicotinic acid (H2cpna), a semi-rigid ligand with
multiple coordination sites. H2cpna has been proven to be
useful in the construction of coordination polymers, which
can be attributed to the different protonated extend depending
on the pH and free rotation of the C–C single bond between
pyridyl and phenyl rings.3
Tel: +86-931-8915196
†Electronic supplementary information (ESI) available: Tables of selected bond
distances and angles, hydrogen bonds in crystal packing of the complexes, 3D
renderings of Fig. S1 and S2, results of the temperature-dependent powder XRD
study of compound 6, luminescent data for complexes
2 and 6. CCDC
900086–900097 for 1–12. For ESI and crystallographic data in CIF or other elec-
tronic format see DOI: 10.1039/c2dt32674d
4822 | Dalton Trans., 2013, 42, 4822–4830
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In this contribution, by using ligand H2cpna, changing the 1392 s, 1257 m, 1158 w, 1132 w, 1099 w, 1055 w, 1026 w,
reaction pH value and the anion of the metal salt, and/or 857 m, 792 m, 754 s, 732 w, 499 w, 429 w. Anal. calcd for
using an auxiliary ligand, a series of lanthanide coordination C38H25N4TbO9 (2): C 54.30, H 3.00, N 6.66%. Found: C 53.95,
polymers {[Ln(Hcpna)(cpna)(phen)]·H2O}n (Ln = Sm (1), Tb (2), H 3.37, N 6.97%. IR (KBr, cm−1): 3424 w, 3054 w, 1687 m,
Ho (3), phen
= 1,10-phenanthroline), {[Sm(Hcpna)(cpna) 1614 s, 1584 s, 1535 w, 1517 w, 1421 m, 1393 s, 1258 m,
(phen)]·2H2O}n (4), {[Ln2(cpna)3(H2O)3]·4H2O}n (Ln = Y (5), 1158 w, 1131 m, 1099 w, 1054 w, 1025 w, 850 m, 791 w, 753 s,
Tb (6), Dy (7), Ho (8)), [Lu2(cpna)3(H2O)2]n (9), {[Y2(cpna)3- 731 m, 498 w, 430 m. Anal. calcd for C38H25N4HoO9 (3):
(phen)2(H2O)]·H2O}n
(10),
and
[Ln(cpna)(phen)(NO3)]n C 53.91, H 2.98, N 6.62%. Found: C 54.32, H 3.26, N 6.38%. IR
(Ln = Tm (11), Lu (12)) were prepared by a hydrothermal (KBr, cm−1): 3423 w, 3052 w, 1687 m, 1616 s, 1583 s, 1537 w,
method. Their structural diversities show that the pH value of 1517 w, 1423 m, 1392 s, 1258 m, 1158 w, 1131 m, 1099 w,
the reaction system, anion, auxiliary ligand and lanthanide 1056 w, 1024 w, 851 m, 791 w, 753 s, 730 m, 684 w, 499 w,
contraction are key factors in the structural self-assembly 431 m.
process.
{[Sm(Hcpna)(cpna)(phen)]·2H2O}n (4). The preparation of 4
was similar to that of 1 except using SmCl3·6H2O instead of
Sm(NO3)3·6H2O. After being cooled to room temperature, col-
orless block-shaped crystals of 4 were isolated manually, and
washed with distilled water. Yield: 48% (based on H2cpna).
Calcd for C38H27N4SmO10: C 53.69, H 3.20, N 6.59%. Found: C
53.31, H 3.46, N 6.25%. IR (KBr, cm−1): 3494 w, 3059 w,
1695 m, 1611 s, 1581 w, 1543 w, 1491 w, 1443 w, 1385 s,
1296 m, 1166 w, 1135 w, 1100 w, 1051 w, 1029 w, 847 m,
810 m, 791 m, 766 m, 726 m, 528 w, 428 m.
{[Ln2(cpna)3(H2O)3]·4H2O}n (Ln = Y (5), Tb (6), Dy (7), Ho
(8)). A mixture of Ln(NO3)3·6H2O (0.2 mmol), H2cpna
(72.9 mg, 0.3 mmol), and H2O (10 mL) was adjusted to pH =
5.5 with 0.5 M NaOH solution. The mixture was stirred at
room temperature for 15 min, and then sealed in a 25 mL
Teflon-lined stainless steel vessel, and heated at 160 °C for
3 days, followed by cooling to room temperature at a rate of
10 °C h−1. Yellow block-shaped crystals were isolated manu-
ally, and washed with distilled water. Yield: 55% for 5, 6; 50%
for 7, 8 (based on H2cpna). Anal. calcd for C39H35N3Y2O19 (5):
C 45.59, H 3.43, N 4.09%. Found: C 45.93, H 3.24, N 4.45%. IR
(KBr, cm−1): 3401w, 3060 w, 1645 w, 1605 s, 1574 w, 1548 m,
1492 w, 1435 m, 1396 s, 1295 w, 1134 w, 1100 w, 1029 w, 953
w, 863 w, 793 w, 762 s, 688 w, 570 w, 431 w. Anal. calcd for
C39H35N3Tb2O19 (6): C 40.12, H 3.02, N 3.60%. Found: C,
40.60; H, 3.36; N 3.90%. IR (KBr, cm−1): 3358 w, 3066 w,
1646 m, 1605 s, 1573 m, 1544 s, 1518 w, 1430 m, 1389 s,
1272 m, 1161 w, 1134 m, 1100 w, 1055 w, 1028 w, 860 m,
794 w, 760 s, 686 m, 566 w, 421 m. Anal. calcd for
C39H35N3Dy2O19 (7): C 39.88, H 3.00, N 3.58%. Found: C 40.21,
H 3.36, N 3.25%. IR (KBr, cm−1): 3369 w, 3065 w, 1647 m,
Experimental
Materials and methods
All chemicals and solvents were of A.R. grade and used
without further purification. Carbon, hydrogen and nitrogen
were determined using an Elementar Vario EL elemental ana-
lyzer. IR spectra were recorded using KBr pellets and a Bruker
EQUINOX 55 spectrometer. Thermogravimetric analysis (TGA)
was performed under N2 atmosphere with a heating rate of
10 °C min−1 on a LINSEIS STA PT1600 thermal analyzer.
Powder X-ray diffraction patterns (PXRD) were determined
with a Rigaku-Dmax 2400 diffractometer using Cu-Kα radiation
(λ = 1.54060 Å), in which the X-ray tube was operated at 40 kV
and 40 mV. Excitation and emission spectra were recorded on
an Edinburgh FLS920 fluorescence spectrometer at room
temperature for the solid samples. The quantum yields of the
complexes were determined by an absolute method using an
integrating sphere (150 mm diameter, BaSO4 coating) from
Edinburgh Instruments FLS920. The lifetime measurement
was measured on an Edinburgh Instruments FLS920 Fluor-
escence Spectrometer with Nd pumped OPOlette laser as the
excitation source. Magnetic susceptibility data were collected
in the 2–300 K temperature range with a Quantum Design
SQUID Magnetometer MPMS XL-7 with a field of 0.1 T. A cor-
rection was made for the diamagnetic contribution prior to
data analysis.
Synthesis of complexes 1–12
{[Ln(Hcpna)(cpna)(phen)]·H2O}n (Ln = Sm (1), Tb (2), Ho 1605 s, 1573 m, 1545 m, 1493 w, 1431 m, 1392 s, 1272 m,
(3)). A mixture of Ln(NO3)3·6H2O (0.2 mmol), H2cpna 1160 w, 1134 m, 1101 w, 1055 w, 1028 w, 954 w, 861 m, 793 w,
(72.9 mg, 0.3 mmol), phen (39.6 mg, 0.2 mmol) and H2O 762 s, 687 m, 569 w, 426 m. Anal. calcd for C39H35N3Ho2O19
(10 mL) was adjusted to pH = 4.0–5.0 with 0.5 M NaOH solu- (8): C 39.71, H 2.99, N 3.56%. Found: C 40.09, H 3.41,
tion. The mixture was stirred at room temperature for N 3.85%. IR (KBr, cm−1): 3360 w, 3064 w, 1647 w, 1605 s, 1573
15 min, and then sealed in a 25 mL Teflon-lined stainless steel w, 1547 s, 1494 w, 1430 m, 1392 s, 1296 m, 1134 w, 1100 w,
vessel, and heated at 160 °C for 3 days, followed by cooling to 1055 w, 1028 w, 862 m, 793 w, 761 s, 687 w, 594 w, 428 m.
room temperature at a rate of 10 °C h−1. Yellow block-shaped
[Lu2(cpna)3(H2O)2]n (9). The preparation of 9 was similar to
crystals were isolated manually, and washed with distilled that of 5 except using Lu(NO3)3·6H2O instead of Y(NO3)3·6H2O.
water. Yield: 60% for 1; 55% for 2; 50% for 3 (based on After being cooled to room temperature, yellow block-shaped
H2cpna). Calcd for C38H25N4SmO9 (1): C 54.86, H 3.03, crystals of 9 were isolated manually, and washed with distilled
N 6.73%. Found: C 55.17, H 3.41, N 6.35%. IR (KBr, cm−1): water. Yield: 50% (based on Lu). Calcd for C39H25N3Lu2O14:
3424 w, 3056 w, 1687 m, 1613 s, 1580 w, 1533 w, 1417 w, C 42.22, H 2.27, N 3.79%. Found: C 42.61, H 2.59, N 3.35%.
This journal is © The Royal Society of Chemistry 2013
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IR (KBr, cm−1): 3360 w, 3052 w, 1603 s, 1578 w, 1552 s, 1491 w, graphite-monochromated Mo Kα radiation (λ = 0.71073 Å).
1441 m, 1400 s, 1294 w, 1267 w, 1158 w, 1100 w, 1026 w, 902 Semiempirical absorption corrections were applied using the
w, 865 m, 814 m, 761 m, 706 m, 685 m, 661 w, 577 w, 424 m.
{[Y2(cpna)3(phen)2(H2O)]·H2O}n (10). A mixture
SADABS program. The structures were solved by direct methods
of and refined by full-matrix least-squares on F2 using the
Y(NO3)3·6H2O (76.6 mg, 0.2 mmol), H2cpna (72.9 mg, SHELXS-97 and SHELXL-97 programs.4 All non-hydrogen atoms
0.3 mmol), phen (39.6 mg, 0.2 mmol), and H2O (10 mL) was were refined anisotropically by full-matrix least-squares
adjusted to pH = 5.5 with 0.5 M NaOH solution. The mixture methods on F2. All the hydrogen atoms (except the those bound
was stirred at room temperature for 15 min, and then sealed in to water molecules) were placed in calculated positions with
a 25 mL Teflon-lined stainless steel vessel, and heated at fixed isotropic thermal parameters and included in structure
160 °C for 3 days, followed by cooling to room temperature at a factor calculations in the final stage of full-matrix least-squares
rate of 10 °C h−1. Yellow block-shaped crystals were isolated refinement. The hydrogen atoms of water molecules were
manually, and washed with distilled water. Yield: 60% (based located by difference maps and constrained to ride on their
on H2cpna). Calcd for C63H41N7Y2O14 (10): C 58.30, H 3.18, N parent O atoms. Crystallographic data as well as details of data
7.55%. Found: C 58.66, H 3.01, N 7.27%. IR (KBr, cm−1): 3422 collection and refinement for these complexes are summarized
w, 3051 w, 1617 s, 1585 s, 1538 m, 1517 w, 1424 m, 1394 s, in Table 1 and Table S1 (ESI†). Important bond lengths bond
1258 m, 1158 w, 1100 m, 1025 w, 851 m, 792 w, 752 m, 732 w, angles are listed in Table S2 (ESI†). Hydrogen bonds in crystal
708 m, 684 w, 605 w, 434 w.
packing for the compounds 1–10 are listed in Table S3 (ESI†).
[Ln(cpna)(phen)(NO3)]n (Ln = Tm (11), Lu (12)). The prep-
aration of 11 and 12 was similar to that of 10 except using Tm-
(NO3)3·6H2O and Lu(NO3)3·6H2O instead of Y(NO3)3·6H2O.
Yield: 50% for 10; 55% for 11 (based on H2cpna). Calcd for Results and discussion
C25H15N4TmO7 (11): C 46.03, H 2.32, N 8.59%. Found: C 45.71,
Description of the structures
H 2.67, N 8.21%. IR (KBr, cm−1): 3384 w, 1615 s, 1576 w, 1519
Structures of 1–3. Single-crystal X-ray diffraction analysis
s, 1392 s, 1286 s, 1144 w, 1101 w, 1027 w, 858 m, 811 m,
765 m, 727 m, 690 w, 661 w, 591 w, 424 w. Calcd for
C25H15N4LuO7 (12): C 45.61, H 2.30, N 8.51%. Found: C 45.29,
H 2.57, N 8.78%. IR (KBr, cm−1): 3366 m, 1617 s, 1578 w, 1520
s, 1420 m, 1394 s, 1348 w, 1288 s, 1144 w, 1101 w, 1028 w,
859 m, 766 w, 727 m, 690 w, 661 w, 592 w, 423 w.
reveals that complexes 1–3 are isostructural 3D frameworks
based on the dodecanuclear Sm/Tb/Ho macrocycles, and the
structure of 1 is selected and described in detail. Complex 1
ˉ
crystallizes in the trigonal space group R3. The asymmetrical
unit of compound 1 contains one crystallographically unique
Sm(III) ion, one Hcpna− ligand, one cpna2− ligand, one phen
ligand, and one lattice water molecule. As shown in Fig. 1a,
Sm(III) ion is nine-coordinated by five carboxylate O atoms of
X-Ray crystallography
The X-ray single-crystal data collection for complexes was four individual cpna2− ligands, two carboxylate O atoms from
performed on a Bruker Smart CCD diffractometer, using one Hcpna− ligand, and two N atoms of one phen ligand,
Table 1 Crystal data and structure refinement parameters for complexes 1, 4, 6, 9–11
Compound
1
4
6
9
10
11
Formula
Formula mass
Crystal system
Space group
C38H25SmN4O9
831.97
C38H27SmN4O10
849.99
Triclinic
ˉ
P1
C39H35Tb2N3O19
1167.54
Triclinic
ˉ
P1
C39H25Lu2N3O14
1109.56
Triclinic
ˉ
P1
C63H41Y2N7O14
1297.85
Triclinic
ˉ
P1
C25H15TmN4O7
652.34
Monoclinic
P21/n
Trigonal
ˉ
R3
a/Å
b/Å
c/Å
α/°
31.18(3)
31.18(3)
18.229(19)
90
120
90
15 353(27)
296(2)
18
9.128(3)
13.654(4)
14.128(4)
97.222(3)
96.653(3)
105.169(3)
1665.5(9)
293(2)
12.788(2)
13.670(2)
14.211(2)
66.1690(10)
66.9470(10)
77.0190(10)
2084.5(6))
296(2)
11.476(2)
12.667(2)
13.512(3)
103.635(2)
99.747(2)
108.5040(10)
1745.5(6)
296(2)
8.371(7)
13.459(11)
24.53(2)
75.911(8)
86.628(8)
79.871(8)
2638(4)
296(2)
2
12.366(8)
10.426(7)
17.438(12)
90
93.717(7)
90
2244(3)
293(2)
4
β/°
γ/°
V/Å3
T/K
Z
2
2
2
Dc/g cm−3
1.620
1.695
1.860
2.111
1.634
1.931
F(000)
7470
17 322
5935
0.0837
1.006
0.0568
0.1292
0.1054
0.1514
850
12 312
6119
0.0493
1.037
0.0412
0.0859
0.0534
0.0919
1144
15 080
7643
0.0324
1.051
0.0305
0.0766
0.0372
1068
12 924
6418
0.0243
1.050
0.0252
0.0467
0.0334
0.0489
1316
18 661
9358
0.0729
1.002
0.0549
0.0966
0.1291
0.1178
1272
15 657
4183
0.0827
1.029
0.0486
0.0996
0.0776
0.1114
Data collected
Unique data
Rint
GOF on F2
R1 (I > 2σ(I))
wR(F2) values (I > 2σ(I))
R1 values (all data)
wR(F2) values (all data)
0.0790
4824 | Dalton Trans., 2013, 42, 4822–4830
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x − y + 2/3, z − 1/3). Two crystallographically equal Sm(III)
centers are bridged by two O atoms of carboxylate groups from
two different cpna2− ligands and two carboxyl groups from two
individual cpna2− ligands in bidentate mode into a binuclear
unit (Fig. S1, ESI†) with a Sm–Sm distance of 4.031(3) Å and
Sm–Ocarboxylate–Sm angle of 107.26(19)°. The binuclear units
are linked by cpna2− ligands forming a dodecanuclear Sm(III)
macrocycle (Fig. 1b). The ring adopts a chair conformation
resembling cyclohexane with the side length of 15.1229(15) Å
(Fig. S2, ESI†). The ring is connected with six adjacent rings by
co-corner forming a regular layer structure in the ab plane
(Fig. 1c and 1d). The layers are further linked by the coordi-
nation interaction of cpna2− ligands and Sm(III) ions to gener-
ate a 3D framework (Fig. S3, ESI†). The dihedral angles of the
pyridyl and the phenyl rings in one Hcpna− ligand are 66.74°
for 1, 66.85° for 2, 67.60 for 3. Those in one cpna2− ligand are
56.29° for 1, 56.81° for 2, 56.94 for 3, respectively.
Structure of 4. Complex 4 crystallizes in the triclinic space
ˉ
group P1 and features a 1D wheel-chain structure based on a
Fig. 1 (a) The coordination environment of the Sm(III) ion in 1. The hydrogen
atoms are omitted for clarity except those bonds to carboxylate oxygen atoms.
Symmetry codes: i = –x + 4/3, −y + 5/3, −z + 2/3; ii = x − y + 1, x, −z + 1; iii = −x
+ y + 1/3, −x + 5/3, z − 1/3. (b) A dodecanuclear Sm(III) macrocycle. The green
balls represent the dinuclear units. The hydrogen atoms are omitted for clarity.
(c) The 2D layer consisting of the hexagonal rings. (d) The representation of the
connection mode among the hexagonal rings. The green balls represent the
dinuclear units.
binuclear unit, which is isotypic with its Pr, Nd, Eu, and Gd
analogues reported by our group.3b The asymmetrical unit of
compound 4 consists of one crystallographically independent
Sm(III) ion, one Hcpna− ligand, one cpna2− ligand, and two
lattice water molecules. Sm(III) ion is nine-coordinated by
seven O atoms and two N atoms, which resembles a distorted
tricapped trigonal geometry (Fig. 2a). The Sm–O bond lengths
range from 2.375(3) to 2.756(4) Å, the Sm–N distances vary
from 2.592(4) to 2.601(4) Å. The Hcpna− ligand adopts coordi-
nation mode III, in which deprotonated carboxylate group
shows μ1–η1:η1 bidentate mode. The cpna2− ligand takes
coordination mode IV, in which two carboxylate groups take
μ2–η1:η1 bidentate mode and μ2–η1:η2 tridentate mode, respect-
ively. It is noted that in 1–4, the related carboxylate groups in
Hcpna− and cpna2− ligands take the same coordination
modes, however, the Hcpna− and cpna2− ligands adopt
different conformations (trans for 1–3 and cis for 4). In 4, the
N atoms of both Hcpna− and cpna2− ligands remain uncoordi-
nated and involved in the interchain hydrogen bonding. Two
crystallographically equal Sm(III) centers are bridged by two O
atoms of carboxylate groups from two different cpna2− ligands
Scheme 1 The various coordination modes for Hcpna−/cpna2− in compounds
1–12. I: trans-1 κ2 O,O’; II: trans-μ4-1 κ2 O,O’:2 κ O:3 κ O’’:4 κ O’’’; III: cis-1 κ2 O,O’;
IV: cis-μ4-1 κ2 O,O’:2 κ O:3 κ O’’:4 κ O’’’; V: cis-μ4-1 κ O:2 κ O’:3 κ O’’:4 κ O’’’; VI:
trans-μ3-1 κ2 O,O’:2 κ O’’:3 κ O’’’; VII: cis-μ3-1 κ O:2 κ O’:3 κ O’’; VIII: trans-μ4-1 κ
O:2 κ O‘:3 κ O’’:4 κ O’’’; IX: trans-μ-1 κ O:2 κ O’.
which resembles a distorted tricapped trigonal geometry. The
Sm–O bond lengths range from 2.391(5) to 2.612(6) Å, the
Sm–N distances vary from 2.616(7) to 2.636(7) Å. The Hcpna−
ligand adopts coordination mode I (Scheme 1), in which the
deprotonated carboxylate group shows μ1–η1:η1 bidentate
mode. The cpna2− ligand takes coordination mode II, in which
two carboxylate groups adopt μ2–η1:η1 bidentate mode and
μ2–η1:η2 tridentate mode, respectively (Scheme 1). It should be
mentioned that in 1–3, the N atoms of both Hcpna− and
cpna2− ligands remain uncoordinated and involved in the
intermolecular hydrogen bonding (O3–H3⋯N2i, i = –y + 4/3,
Fig. 2 (a) The coordination environment of the Sm(III) ion in 4. The hydrogen
atoms are omitted for clarity except those bonds to oxygen atoms of the carboxy-
late groups. Symmetry codes: i = −x + 2, −y + 1, −z; ii = −x + 1, −y + 1, −z; iii =
x − 1, y, z. (b) Views of the 1D wheel chain along the ab plane. The hydrogen
atoms are omitted for clarity except those bonds to oxygen atoms of the carboxy-
late groups.
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and two carboxyl groups from two individual cpna2− ligands in modes II, V and VI), in which carboxylate groups show μ1–η1:η1
bidentate mode into a dimeric unit with a Sm–Sm distance of bidentate mode, μ2–η1:η1 bidentate mode, and μ2–η1:η2 triden-
4.001(2) Å and Sm–Ocarboxylate–Sm angle of 102.21(12)°, which tate mode, respectively. The dihedral angles of the pyridyl and
is further joined by cpna2− ligands to form a 1D wheel-chain the phenyl rings in the cpna2− ligands are 35.46°, 56.96° and
structure (Fig. 2b). The 1D chains are further extended into a 50.51°, respectively. Adjacent Tb atoms are bridged by O atoms
3D metal–organic supramolecular framework by O–H⋯N of carboxylate groups and carboxyl groups into a [Tb12Tb22]
hydrogen-bonding interactions (Table S3, Fig. S4, ESI†). The tetranuclear unit (Fig. S5, ESI†). The tetranuclear units are
dihedral angles of the pyridyl and the phenyl rings in one further linked by the coordination interaction of cpna2−
Hcpna− ligand and one cpna2− ligand are 73.32° and 69.74°, ligands and Tb(III) ions to generate a open 3D framework
respectively.
(Fig. 3c). The dimension of each channel is 5.63 Å × 11.0 Å
5.63,
Structures of 5–8. Compounds 5–8 are isostructural and measured by atom-to-atom distances (N3⋯N3i
=
feature a three-dimensional open framework structure. Hence, Tb2⋯Tb2i = 11.0 Å, i = x + 2, y + 2, z). The N atoms of cpna2−
only the structure of 6 is selected and described in detail. ligands point toward the open channel. The channels are filled
ˉ
Complex 6 crystallizes in the triclinic space group P1. In the with guest water molecules. Viewed down the b-axis (Fig. S6,
asymmetrical unit, there are two crystallographically unique ESI†), the framework of compound 6 also displays long narrow
Tb(III) atoms, three cpna2− ligands, three coordinated water shaped channels with size about 15.2 Å × 10.6 Å measured by
and four lattice water molecules. As depicted in Fig. 3a, Tb1 atom-to-atom distances (Tb2⋯Tb2ii = 15.2 Å, C30⋯C30ii
=
atom is eight-coordinated by seven carboxylate O atoms of six 5.63, ii = x + 1, y + 2, z). When removing guest water molecules,
different cpna2− ligands, and one O atom of one coordinated we computed its effective free volume as being 18.2% by
water molecule, constructing a distorted bicapped trigonal PLATON analysis of the crystal volume.5 If removing both coor-
prism. Tb2 atom is also eight-coordinated by six carboxylate O dinated waters and guest water molecules, the effective free
atoms of five independent cpna2− ligands, and two O atoms of volume of compound 6 is calculated by PLATON analysis as
two coordinated water molecules, forming
a distorted being 21.1% of the crystal volume.
bicapped trigonal prism (Fig. 3b). The lengths of Tb–O bonds
Structure of 9. Complex 9 crystallizes in the triclinic space
are in the range of 2.248(3)–2.528(3) Å. The cpna2− ligands group P1. The asymmetrical unit of compound 9 contains two
adopt three different coordination modes (Scheme 1, crystallographically unique Lu(III) atoms, three cpna2− ligands,
and two coordinated water molecules. As shown in Fig. 4a, Lu1
ˉ
atom is eight-coordinated by seven carboxylate O atoms of six
Fig. 4 (a) The coordination environment of the Lu1 ion in 9. The hydrogen
atoms are omitted for clarity except those bonds to oxygen atoms of the coordi-
Fig. 3 (a) The coordination environment of the Tb1 ion in 6. The hydrogen
atoms are omitted for clarity except those bound to oxygen atoms of the coordi-
nated water molecules. Symmetry codes: i = −x, −y + 2, −z + 2; ii = x, y, z + 1;
iii = −x + 1, −y + 2, −z + 1; iv = −x + 1, −y + 2, −z + 2. (b) The coordination
environment of the Tb2 ion in 6. The hydrogen atoms are omitted for clarity
except those bound to oxygen atoms of the coordinated water molecules. Sym-
metry codes: i = −x, −y + 2, −z + 2; iii = −x + 1, −y + 2, – z+ 1; v = –x + 1, –y + 1,
–z + 2. (c) A perspective of 3D framework along the bc plane. The hydrogen
atoms and water molecules are omitted for clarity.
nated water molecules. Symmetry codes: i = −x + 1, −y + 1, −z + 2; ii = −x + 1,
−y, −z + 1; iii = −x + 1, −y + 1, −z + 1. (b) The coordination environment of the
Lu2 ion in 9. The hydrogen atoms are omitted for clarity except those bound to
oxygen atoms of the coordinated water molecules. Symmetry codes: i = −x + 1,
−y + 1, −z + 2; ii = −x + 1, −y, −z + 1; vi = −x + 2, −y + 1, −z + 2. (c) Tetranuclear
unit. The hydrogen atoms are omitted for clarity. The hydrogen atoms are
omitted for clarity except those bound to oxygen atoms of the coordinated
water molecules. Symmetry code: i = −x + 1, −y + 1, −z + 1; ii = −x + 2, −y + 1,
−z + 2.
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individual cpna2− ligands, and one O atom of one coordinated show μ2–η1:η1 bidentate mode, and μ2–η1:η2 tridentate mode,
water molecule, forming a distorted bicapped trigonal prism. and μ1–η1:η0 monodentate mode, respectively. The dihedral
Lu2 atom is six-coordinated by five carboxylate O atoms of five angles of the pyridyl and the phenyl rings in the cpna2−
independent cpna2− ligands, and one O atom of one coordi- ligands are 59.75°, 57.17° and 44.99°, respectively. Two crystal-
nated water molecule, constructing a distorted octahedral geo- lographically equal Y1 centers are bridged by four carboxyl
metry (Fig. 4b). The distances of Lu–O span the range of 2.127 groups from four individual cpna2− ligands in bidentate mode
(4)–2.503(3) Å. The cpna2− ligands adopt three different coordi- into a binuclear unit (Fig. S8, ESI†) with a Y1–Y1 distance of
nation modes coordination (Scheme 1, modes II, VII and VIII), 4.301(3) Å. Meanwhile, two crystallographically equal Y2 atoms
in which carboxylate groups show μ2–η1:η1 bidentate mode, are bridged by two O atoms of carboxylate groups from two
μ2–η1:η2 tridentate mode, and μ1–η1:η0 monodentate mode, different cpna2− ligands and two carboxyl groups from two
respectively. The dihedral angles of the pyridyl and the phenyl individual cpna2− ligands in bidentate mode into a dimeric
rings in the cpna2− ligands are 39.33°, 77.24° and 70.82°, unit (Fig. S9, ESI†) with a Y2–Y2 distance of 3.876(2) Å. These
respectively. Adjacent Lu atoms are bridged by O atoms of car- dimeric units are joined by cpna2− ligands to form 1D chains,
boxylate groups and carboxyl groups into a [Lu12Lu22] tetra- which further connected by the cpna2− ligands to construct 2D
nuclear unit (Fig. 4c). The tetranuclear units are further linked sheet (Fig. S10, ESI†). The sheets are extended into a 3D
by the coordination interaction of cpna2− ligands and Lu(III) metal–organic framework by the coordination interaction of
ions to generate a 3D framework (Fig. S7, ESI†).
cpna2− ligands and Y(III) ions (Fig. 5c).
Structure of 10. Complex 10 crystallizes in the triclinic space
Structures of 11 and 12. X-Ray single crystal diffraction ana-
ˉ
group P1. The asymmetrical unit of compound 10 consists of lyses reveal that complexes 11 and 12 are also isostructural
two crystallographically unique Y(III) atoms, three cpna2− and feature a 1D chain structure, hence, only the structure of
ligands, two phen ligands, one coordinated water and one 11 is described in detail here. Complex 11 crystallizes in the
lattice water molecule. As shown in Fig. 5a and 5b, both Y1 monoclinic space group P21/n. In the asymmetrical unit, there
and Y2 ions are eight-coordinated in a distorted bicapped tri- is one crystallographically unique Tm(III) atom, one cpna2−
gonal prism geometry. Y1 ion is coordinated by five carboxy- ligand, one phen ligand, one nitrate ligand. As shown in
late O atoms of five individual cpna2− ligands, two N atoms Fig. 6a, Tm(III) ion has an eight-coordinate environment, six of
from one phen ligand, and one O atom of one coordinated which are occupied by four O atoms of carboxyl groups from
water molecule, while Y2 ion is bonded to six carboxylate three individual cpna2− ligands and two O atoms from one
O atoms of five independent cpna2− ligands, and two N atom nitrate ligand, and the remaining two sites are occupied by
of one phen ligand. The distances of Y–O and Y–N bonds span two N atoms of one phen ligand, forming a distorted bicapped
the range of 2.175(4)–2.551(4) Å and 2.529(5)–2.557(5) Å. The trigonal prism. The Tm–O distances range from 2.208(6) to
cpna2− ligands adopt three different coordination modes 2.412(7) Å, the Tm–N distances vary from 2.475(7) to
(Scheme 1, modes IV, V and IX), in which carboxylate groups 2.498(6) Å. All the Ln–O and Ln–N distances in compounds
1–12 are comparable to those reported for other Ln–O and Ln–
N donor complexes.1e,f,h,j,l,q,6 The cpna2− ligand takes coordi-
nation mode VI, in which two carboxylate groups take μ1–η1:η1
and μ2–η1:η1 bidentate modes, respectively. In this way, cpna2−
ligands linked neighboring Tm(III) ions to yield an 1D double
chain along the c axis (Fig. 6b). The dihedral angle of the
pyridyl and the phenyl rings in the cpna2− ligand is 62.16°.
The chains are further extended into a 3D metal–organic
Fig. 5 (a) The coordination environment of the Y1 ion in 10. The hydrogen
atoms are omitted for clarity. Symmetry codes: i = −x, −y + 2, −z + 1; ii = −x − 1,
−y + 2, −z + 1; iii = x + 1, y, z. (b) The coordination environment of the Y2 ion in
10. The hydrogen atoms are omitted for clarity. Symmetry codes: iv = −x + 1,
−y + 1, −z; v = x − 1, y, z; vi = −x, −y + 1, −z. (c) A perspective of 3D framework
along the bc plane. The hydrogen atoms are omitted for clarity.
Fig. 6 (a) The coordination environment of the Tm ion in 11. The hydrogen
atoms are omitted for clarity. Symmetry codes: i = −x + 1, −y + 2, −z; ii = x, y − 1,
z. (b) 1D double chain along the c axis. The hydrogen atoms are omitted for
clarity.
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supramolecular framework (Fig. S11, ESI†) by C–H⋯O hydro-
gen bond (C17i–H17i⋯O5, C17i⋯O5 = 3.636(10) Å, C3ii–
H3ii⋯O6, C3ii⋯O6 = 3.336(11) Å, C6iii–H6iii⋯O7, C6iii⋯O7 =
3.463(10) Å, i = –x + 0.5, y − 0.5, −z − 0.5, ii = –x + 0.5, y − 0.5,
−z + 0.5, iii = x − 0.5, −y + 1.5, z − 0.5; Table S3, ESI†).
Structural diversity
Complexes 1–12 were successfully synthesized by reacting
H2cpna ligand (auxiliary ligand phen for 1–4 and 10–12) with
the corresponding lanthanide salts at 160 °C for 3 days under
hydrothermal conditions, as shown in Scheme 2. From the
above description of crystal structures, it can be found that
complexes 1–12 exhibit six different structures. On the basis of
the structures, it was noted that the influence of the pH value
on the structures is in fact based on the protonated extend of
H2cpna ligand. For example, at pH = 4–5, partially deproto-
nated Hcpna− and completely deprotonated cpna2− forms
coexist in 1–4. When pH value is adjusted to 5.5, only cpna2−
form is observed in 5–12. Complexes 1 and 4 were synthesized
under the same reaction conditions, except for the samarium
salts (Sm(NO3)3·6H2O for 1 and SmCl3·6H2O for 4). Their struc-
tural differences ambiguously indicate that the assembly
process is anions-dependent. The different anions induce the
Hcpna− and cpna2− ligands to adopt different conformations
(trans for 1 and cis for 4), which result in different structures,
that is, 1 shows 3D framework and 4 exhibits a 1D wheel-chain
structure. The structural difference between 2 and 6 is ascribed
to the different reaction pH (pH = 4–5 for 2 and 5.5 for 6) and
adding auxiliary ligand phen in 2. The structural change
between 5 and 10 (9 and 12) caused by adding auxiliary ligand
phen in 10 (12) under the same reaction conditions. Com-
plexes 10–12 were isolated under the same reaction conditions
except using different lanthanide nitrates (Y(NO3)3·6H2O for
10, Tm(NO3)3·6H2O for 11, and Lu(NO3)3·6H2O for 12), which
result in different structures, that is, 10 show 3D framework
and 11 and 12 possess a 1D double chain structure. It is the
lanthanide contraction effect that results in forming the
different crystal structures. In 10, the larger Y(III) ion can coor-
dinate to five cpna2− anions, one phen ligand, and/or one
water molecule, while the smaller Tm(III) and Lu(III) ions in 11
and 12 can only coordinate to three cpna2− anions and one
phen ligand due to steric effects (Fig. 5a, 5b and 6a). Mean-
while, one Tm(III)/Lu(III) ion coordinated to one bidentate
nitrate ligand for satisfaction with the coordination number
and charge balance. These results imply that the reaction con-
ditions including pH value, anions, auxiliary ligand and metal
Fig. 7 Thermogravimetric analyses (TGA) curves of compounds 1, 4, 6, and
9–11.
ionic radii could well tune the structures of lanthanide coordi-
nation polymers.
Thermal analysis
To further determine the thermal stability of compounds 1–12,
their thermal behaviors were investigated under nitrogen
atmosphere by TGA. The results indicate that complexes 1–3
(5–8, 11 and 12) show similar thermal behavior owing to their
isomorphous structures; thus only the thermal stabilities of
complexes 1, 4, 6, and 9–11 are discussed in detail (Fig. 7).
Compound 1 lost its one lattice water molecule (exptl, 2.46%;
calcd, 2.16%) from 60 to 160 °C, and then decomposition
occurs at 342 °C. For complex 4, there is one distinct weight
loss procedure in the range of 70–165 °C, corresponding to the
loss of two free water molecules per formula unit (exptl,
4.60%; calcd, 4.24%). The remaining structure was broken
down at 330 °C.
Compound 6 lost its four lattice water and three coordi-
nated water molecules (exptl, 10.7%; calcd, 10.8%) from 60 to
230 °C, and then decomposition occurs at 450 °C. For com-
pound 9, the weight loss corresponding to the release of two
coordinated water molecule was observed from 120 to 220 °C
(exptl, 3.65%; calcd, 3.24%), and the decomposition of the
residue was observed at about 400 °C. The TGA curves of com-
pounds 10 and 11 show their frameworks were stable up to
350 °C and 345 °C, respectively. Then, the frameworks began
to decompose upon further heating.
Dehydration/hydration study
To study the dehydration/hydration properties of compounds
5–8, compound 6 was heated to different temperatures (120
and 180 °C) for 3 h and then was treated with water (Fig. S12,
ESI†). The XRD patterns indicate that the structure of com-
pound 6 can be kept after heating at 180 °C, and the structure
transformation occurs at 200 °C. Interestingly, when the cal-
cined samples at 180 °C were suspended in water overnight,
and then, the solid was filtered off and dried at room tempera-
ture, the same XRD patterns as those of the original crystal
were regenerated. Thus, the dehydrated solids of these com-
pounds may potentially be reversible adsorbent materials for
water molecules.
Scheme 2 Synthetic strategy of compounds 1–12.
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Fig. 8 Solid state emission spectra of compounds
2 and 6 at room
temperature.
Luminescent properties
Lanthanide-containing compounds are interesting lumines-
cence materials because they emit over the entire spectral
range. Especially Tb(III) compounds show strong and character-
istic luminescent emissions in the visible region upon exci-
tation of ultraviolet radiation, making them good candidate
materials for luminescent probes.7 The solid-state lumines-
cence properties of compounds 2 and 6 were investigated at
room temperature (Table S4, ESI†). As illustrated in Fig. 8,
upon excitation at 331 and 312 nm, compounds 2 and 6 show
the characteristic emission pattern of the Tb(III) ion. The
strong emission lines at 489/488, 544/542, 584/582, and
622/621 nm are assigned to transitions between the first
○
□
) vs. T for compounds
Fig. 9 Temperature dependence of χMT ( ) and 1/χM
(
1, 3, 4, 7 and 11. The black lines show the Curie–Weiss fitting.
5
7
excited state, D4, and the ground state multiplet FJ (J = 6, 5,
4, 3). It is noteworthy that compound 2 exhibits stronger emis-
sion intensities than compound 6, which can be attributed to
their different structures. In compound 2, the phen ligands
were introduced, which increased the efficiency of the energy
transfer from the ligands to Tb(III) ions.8,9 Meanwhile, coordi-
nated water and lattice water molecules in 6 play a part in the
quenching effect of the luminescent state.7,10 Upon removal of
the water molecules at 180 °C for 3 h, the intensity of the emis-
sion bands for the dehydrated sample are enhanced by a factor
of approximately two. The luminescence of the re-hydrated
sample returned to its original level. This process was rever-
sible. Compound 6 shows promise as a luminescent probe to
detect water.
of Sm3+ coming from the strong unquenched orbital angular
momentum.12,13
For 3, at 300 K, the χMT value of 14.6 cm3 mol−1 K is close
to the value expected (14.1 cm3 mol−1 K) for one insulated Ho
(III) ion (S = 2, L = 6, 5I8, g = 5/4). χMT value gradually decreases
to reach 5.74 cm3 mol−1 K at 2 K. Between 2 and 300 K, the
magnetic susceptibilities can be fitted to the Curie–Weiss law,
χM = CM/(T − θ), with CM = 15.4 cm3 K mol−1, θ = −15.9 K. On
account of the larger spin–orbit coupling of Ho3+, these results
can not be exactly ascribed to the antiferromagnetic inter-
actions between the adjacent Ho(III) centers.
For 7, at 300 K, χMT is equal to 28.5 cm3 mol−1 K, which is
close to the value expected (28.3 cm3 mol−1 K) for two Dy(III)
6
(S = 5/2, L = 5, H15/2, g = 4/3). Upon lowering the temperature,
Magnetic properties
the χMT value decreases continuously to
a value of
Variable-temperature magnetic susceptibility measurements 23.4 cm3 mol−1 K at 2 K. Between 2 and 300 K, the magnetic
were performed on powder samples of 1, 3, 4, 7 and 11 in the susceptibilities can be fitted to the Curie–Weiss law with CM
=
temperature range of 2–300 K (Fig. 9). For 1 and 4, as shown in 29.0 cm3 K mol−1, θ = −6.53 K. On account of the larger spin–
Fig. 9, the χMT values at room temperature are orbit coupling of Dy3+, these results do not indicate a weak
0.221 cm3 mol−1 K for 1 and 0.258 cm3 mol−1 K for 4, which antiferromagnetic interaction between the neighboring Dy(III)
are larger than that (0.088 cm3 mol−1 K) expected for one mag- ions.
netically isolated Sm(III) ion (S = 5/2, L = 5/2, H5/2, g = 2/7),
For 11, at 300 K, the χMT value of 7.29 cm3 mol−1 K is close
6
because not only the ground state of the Sm(III) ion but also to the value expected (7.14 cm3 mol−1 K) for one magnetically
3
the first (6H7/2) and even highly exited states can be populated isolated Tm(III) ion (S = 1, L = 5, H6, g = 7/6). As the temper-
at room temperature.11 The monotonic decrease in χMT with ature is lowered, the χMT value gradually increases to reach a
cooling temperature is not indicative of dominant antiferro- dispersed maximum of 7.83 cm3 K cm−1 at T ≈ 78 K and then
magnetic interaction because of the strong spin–orbit coupling abruptly decreases to the value of 3.78 cm3 K mol−1 at 2 K.
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The maximum χMT value may be related to a ferromagnetic
exchange between the magnetic centers. Between 80 and
300 K, the magnetic susceptibilities can be fitted to the Curie–
Weiss law with CM = 7.06 cm3 mol−1 K, θ = 9.64 K.
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Conclusions
In this work, by adjusting the reaction pH value and/or using
auxiliary ligand, a series of lanthanide coordination com-
pounds based on H2cpna ligand were synthesized by a hydro-
thermal method. These compounds possess 1D and 3D
frameworks with different architectures. Their structural diver-
sities demonstrate that the pH value of the reaction system,
anion, auxiliary ligand and lanthanide contraction play a
crucial role in determination of the structures of the coordi-
nation polymers. Luminescent measurements indicate the
compound 6 is a potential luminescent sensor material.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Project 20931003, 21071068)
and the Fundamental Research Funds for the Central Univer-
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