A family of coordination polymers assembled with a flexible hexacarboxylate ligand and auxiliary N-donor ligands: Syntheses, structures, and physical properties

Article abstract of DOI:10.1039/c5ce00181a

Nine new coordination polymers, namely, [Mn₅(HL)₂(H₂O)₂]·2C₂H₅OH·4H₂O (1), Mn₃(L)(phen)₂ (2), Mn₃(L)(2,2′-bpy)₂ (3), Cd₃(L)(2,2′-bpy)₂ (4), Cd₃(L)(phen)₂ (5), Co₂Na(HL)(phen)₂·0.5C₂H₅OH·H₂O (6), Co₃(L)(4,4′-bpy) (7), Cu₂(H₂L)(4,4′-bpy)₄·0.5H₂O (8) and Cu₂(H₂L)(ttp)₂·2C₂H₅OH·2H₂O (9), have been synthesized under hydrothermal conditions (H₆L = 1,2,3,4,5,6-hexakis(3-carboxyphenyloxymethylene)benzene, phen = 1,10-phenathroline, 2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine and ttp = 2-(6-(pyridin-2-yl)-4-p-tolylpyridin-2-yl)pyridine). Compound 1 shows a 2D layer structure. Compounds 2-5 display similar 2D networks, which are further extended into a 3D supramolecular architecture by π-π interactions. Compound 6 exhibits a 3D binodal 4-connected framework with (4²6³8)₂ topology. Compound 7 furnishes a 3D (4,6)-connected framework with (4⁴6²)(4⁴6¹⁰8) topology. Compound 8 reveals a 3D 4-connected framework with 6⁶ topology. Compound 9 displays a 1D chain structure, which is further linked by hydrogen-bonding interactions to yield a 3D supramolecular architecture. Moreover, the diffuse reflectivity spectra of all the compounds, the solid state photoluminescence properties of compounds 4-5, and magnetic properties of compounds 1, 3, 6 and 7 were studied. This journal is

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PAPER
A family of coordination polymers assembled with
a flexible hexacarboxylate ligand and auxiliary
N-donor ligands: syntheses, structures, and
physical properties†
Cite this: CrystEngComm, 2015, 17,
181
3
Hong-Mei Zhang, Jin Yang,* Ying-Ying Liu, Da-Wei Kang and Jian-Fang Ma*a
a
a
a
ab
Nine new coordination polymers, namely, ijMn
Mn IJL)IJ2,2′-bpy) (3), Cd IJL)IJ2,2′-bpy) (4), Cd IJL)IJphen)
Co IJL)IJ4,4′-bpy) (7), Cu IJH L)IJ4,4′-bpy) Ĵ0.5H O (8) and Cu
synthesized under hydrothermal conditions
carboxyphenyloxymethylene)benzene, phen = 1,10-phenathroline, 2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy =
,4′-bipyridine and ttp = 2-IJ6-IJpyridin-2-yl)-4-p-tolylpyridin-2-yl)pyridine). Compound 1 shows a 2D layer
structure. Compounds 2–5 display similar 2D networks, which are further extended into 3D
supramolecular architecture by π–π interactions. Compound 6 exhibits a 3D binodal 4-connected frame-
5
IJHL)
2
IJH
2
O)
(5), Co
IJH L)IJttp)
(H
2
]Ĵ2C
2
H
5
OHĴ4H
NaIJHL)IJphen)
Ĵ2C OHĴ2H
1,2,3,4,5,6-hexakisIJ3-
2
O
(1), Mn
3
IJL)IJphen)
2
(2),
3
2
3
2
3
2
2
2 2
Ĵ0.5C H
5 2
OHĴH O
(6),
3
2
2
4
2
2
2
2
2
H
5
2
O (9), have been
6
L
=
4
a
2
3
4
2
4 10
work with IJ4 6 8)
2
topology. Compound 7 furnishes a 3D (4,6)-connected framework with IJ4 6 )IJ4 6 8)
6
Received 26th January 2015,
Accepted 16th March 2015
topology. Compound 8 reveals a 3D 4-connected framework with 6 topology. Compound 9 displays a 1D
chain structure, which is further linked by hydrogen-bonding interactions to yield a 3D supramolecular
architecture. Moreover, the diffuse reflectivity spectra of all the compounds, the solid state photo-
luminescence properties of compounds 4–5, and magnetic properties of compounds 1, 3, 6 and 7 were
studied.
DOI: 10.1039/c5ce00181a
www.rsc.org/crystengcomm
contrast, the flexible aromatic multicarboxylate ligands have
received relatively less attention. In this regard, the flexible
Introduction
Coordination polymers (CPs) have attracted much attention
owing to their intriguing structural diversity and potential
applications in catalysis, gas sorption or separation, molecu-
1,2,3,4,5,6-hexakisIJ3-carboxyphenyloxymethylene)benzene
(H L) is an excellent ligand for constructing CPs with fascinat-
ing structures and properties (Scheme 1). Typically, the flexi-
6
5
d
1
–6
lar recognition, ion exchange, fluorescence and magnetism.
bility of the –CH – and –O– spacers in the H L allows the car-
2
6
Several factors, such as the reaction temperature, solvents,
templates, pH, metal ions and organic ligands, can influence
the self-assembly of CPs. Among these factors, multicarboxy-
boxylate groups to bridge metal ions in different directions.
On the other hand, the CPs with mixed multicarboxylate and
N-donor ligand have received increasing attention in recent
years. The introduction of the N-containing auxiliary ligands
7
late ligands have been extensively selected as organic anions
in constructing CPs with fascinating structural motifs and
8
properties because of their versatile coordination fashions.
Particularly, the rigid aromatic dicarboxylate, tricarboxylate
and tetracarboxylate have been widely utilized as the organic
anions and yield a large number of functional CPs. In
a
Key Lab of Polyoxometalate Science, Department of Chemistry, Northeast
Normal University, Changchun 130024, People's Republic of China.
E-mail: yangj808@nenu.edu.cn, majf247@yahoo.com; Fax: +86 431 85098620
b
College of Chemistry and Chemical Engineering, Inner Mongolia University for
the Nationalities, Tongliao, 028000, People's Republic of China
†
Electronic supplementary information (ESI) available: CIF files, selected bond
lengths and angles, the coordination spheres of MnIJII) in 3–5, the 2D layers of
3–5, the 3D supramolecular architectures of 3–5 formed by π–π stacking. CCDC
1045517–1045525. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/c5ce00181a
6
Scheme 1 Structure of the H L ligand used in this work.
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into the metal-multicarboxylate system can usually result in a
based on MnIJII). Anal. calcd for C112H Mn O (M = 2422.64):
98
5
44
r
−1
9–11
drastic structure change and property variation.
In this work, the flexible H L ligand and rigid auxiliary
C, 55.53; H, 4.08. Found: C, 55.68; H, 3.97. IR (cm ): 3749(w),
3443(m), 3339(m), 1699(w), 1554(s), 1488(m), 1438(m), 1400(s),
1284(m), 1232(m), 1117(w), 1076(w), 1013(m), 991(m), 928(w),
865(w), 797(w), 766(m), 681(w), 544(w), 439(w).
6
N-containing ligands were elaborately chosen to construct new
CPs. Nine new CPs, namely, ijMn IJHL) IJH O) ]Ĵ2C H OHĴ4H O
5
2
2
2
2
5
2
(
1), Mn
3
IJL)IJphen)
2
(2), Mn
3
IJL)IJ2,2′-bpy)
2
(3), Cd
3
IJL)IJ2,2′-bpy)
2
(4),
Synthesis of Mn
3
IJL)IJphen)
2
(2).
A
mixture of
Cd IJL)IJphen) (5), Co NaIJHL)IJphen) Ĵ0.5C H OHĴH O (6), Co IJL)-
MnIJCH COO) Ĵ4H O (0.025 g, 0.01 mmol), H L (0.033 g,
3
2
2
2
2
5
2
3
3
2
2
6
IJ4,4′-bpy) (7), Cu IJH L)IJ4,4′-bpy) Ĵ0.5H O (8) and Cu IJH L)-
0.033 mmol), phen (0.020 g, 0.01 mmol), ethanol (5 mL), and
water (3 mL) was placed in a Teflon-lined reactor (15 mL)
and heated at 140 °C for 3 days. After gradually cooling to
2
2
4
2
2
2
2 2 5 2
IJttp) Ĵ2C H OHĴ2H O (9), have been hydrothermally synthesized
by using the H L ligand and different rigid N-donor ligands
6
−
1
(phen = 1,10-phenathroline, 2,2′-bpy = 2,2′-bipyridine and ttp =
room temperature at a rate of 10 °C h , colorless crystals of
2 were achieved in 31% yield based on MnIJII). Anal. calcd for
C H O N Mn (M = 1498.08): C, 62.54; H, 3.50; N, 3.74.
2-IJ6-IJpyridin-2-yl)-4-p-tolylpyridin-2-yl)pyridine). All the com-
pounds were characterized by X-ray crystallography, elemental
analysis, infrared spectra (IR), powder X-ray diffraction (PXRD)
and thermogravimetric analyses (TGA). In addition, the effects
7
8
52 18
4
3
r
−
1
Found: C, 62.62; H, 3.59; N, 3.63. IR (cm ): 3421(w), 3066(w),
2902(w), 1611(m), 1572(s), 1513(m), 1489(m), 1437(s), 1422(m),
1397(s), 1341(m), 1311(m), 1280(m), 1233(s), 1139(w), 1120(m),
1101(m), 1072(w), 1054(w), 1012(m), 991(m), 932(w), 863(w),
846(m), 795(m), 766(m), 726(m), 683(m), 667(w), 635(w), 421(w).
of coordination modes of H L and N-donor ligands on the struc-
6
tures of the CPs have been discussed in detail. Furthermore, the
photoluminescence properties for compounds 4–5 and magnetic
properties for compounds 1, 3, 6 and 7 have also been
investigated.
Synthesis of Mn IJL)IJ2,2′-bpy)
(3). mixture of
A
3
2
MnIJCH
3
COO)
2
Ĵ4H
2
O (0.025 g, 0.01 mmol), H L (0.033 g, 0.033
6
mmol), 2,2′-bpy (0.016 g, 0.01 mmol), ethanol (4 mL), and water
(4 mL) was placed in a Teflon-lined reactor (15 mL) and heated
at 150 °C for 3 days. After gradually cooling to room temperature
Experimental section
Materials and methods
−1
at a rate of 10 °C h , colorless crystal products were isolated in
6
The H L ligand was synthesized in accordance with the proce-
2
1
3
2
1
3% yield based on MnIJII). Anal. calcd for C H Mn N O (M =
74 52 3 4 18 r
5d
dure reported. All other reagents and solvents for syntheses
were purchased from commercial sources and used as received.
450.03): C, 61.29; H, 3.61; N, 3.86. Found: C, 61.55; H, 3.55; N,
−1
.93. IR (cm ): 3838(w), 3733(w), 3674(w), 3444(w), 3069(w),
901(w), 1600(m), 1574(s), 1471(m), 1438(s), 1398(s), 1312(m),
281(w), 1232(m), 1153(w), 1120(w), 1055(w), 1014(m), 990(m),
General characterization and physical measurements
The FT-IR spectra were recorded from KBr pellets in the range
935(w), 871(w), 797(w), 766(m), 739(w), 683(w), 543(w), 440(w).
−1
of 4000–400 cm on a Mattson Alpha-Centauri spectrometer.
The powder X-ray diffraction patterns of the samples were col-
lected using a Rigaku Dmax 2000 X-ray diffractometer with
graphite monochromatized Cu Kα radiation (λ = 0.154 nm) and
Synthesis of Cd IJL)IJ2,2′-bpy) (4). The preparation of 4 was
3
2
similar to that of 3 except that CdIJCH
EtOH/H O IJv/v = 7/1) were used instead of MnIJCH
and mixed EtOH/H O IJv/v = 4 : 4). After gradually cooling to
3 2 2
COO) Ĵ2H O and mixed
2
3
COO) Ĵ4H O
2
2
2
−1
2θ ranging from 5 to 50° at room temperature. Microanalyses of
room temperature at a rate of 10 °C h , colorless crystals were
isolated in 25% yield based on CdIJII). Anal. calcd for
C H Cd N O (M = 1622.45): C, 54.78; H, 3.23; N, 3.45.
C, H, and N for the compounds were obtained using a Perkin-
Elmer 2400CHN elemental analyzer. Thermogravimetric analysis
was performed using a Perkin-Elmer TG-7 analyzer heated from
7
4
52
3
4
18
r
−1
Found: C, 54.95; H, 3.29; N, 3.51. IR (cm ): 3856(w), 3750(w),
3674(w), 3650(w), 3444(w), 3340(w), 3068(w), 1715(w), 1598(m),
1561(s), 1474(m), 1438(s), 1390(s), 1312(m), 1281(m), 1230(m),
1118(w), 1055(w), 1015(m), 990(w), 936(w), 806(w), 766(m),
739(w), 682(w), 550(w), 421(w).
2
5 to 600 °C under nitrogen atmosphere with a heating rate of
−1
10 °Cmin . Diffuse reflectance spectra were collected from a
finely ground sample using a Cary 500 spectrophotometer
equipped with a 110 mm diameter integrating sphere, which
were measured from 200 to 800 nm using barium sulfate
Synthesis of Cd IJL)IJphen) (5). The preparation of 5 was
3
2
(BaSO4) as a standard with 100% reflectance. Variable-
similar to that of 3 except that phen was used instead of 2,2′-
temperature magnetic susceptibility data were obtained using a
SQUID magnetometer (Quantum Design, MPMS-5) with an
applied field of 1000 Oe in the temperature range of 2–300 K.
The photoluminescence properties of the compounds were mea-
sured using a Perkin-Elmer FLSP920 Edinburgh fluorescence
spectrometer at room temperature.
bpy. After gradually cooling to room temperature at a rate of
−
1
10 °C h , compound 5 was achieved as colorless crystals in
18% yield based on CdIJII). Anal. calcd for C78
(M = 1670.50): C, 56.08; H, 3.14; N, 3.35. Found: C, 56.46; H,
H
3 4 18
52Cd N O
r
−
1
3.20; N, 3.27. IR (cm ): 3838(w), 3749(w), 3649(w), 3626(w),
3525(w), 3444(w), 3276(w), 3063(w), 1701(w), 1651(w), 1567(s),
1434(m), 1392(s), 1310(m), 1231(m), 1101(w), 1052(w),
1012(m), 989(w), 934(w), 847(m), 800(w), 766(m), 725(m),
683(w), 548(w), 421(w).
5 2 2 2 2 5 2
Synthesis of ijMn IJHL) IJH O) ]Ĵ2C H OHĴ4H O (1). A mixture
of MnIJCH COO) Ĵ4H O (0.025 g, 0.01 mmol), H L (0.033 g,
3
2
2
6
0.033 mmol), ethanol (4 mL), and water (4 mL) was placed in a
Teflon-lined reactor (15 mL) and heated at 140 °C for 3 days.
After gradually cooling to room temperature at a rate of 10 °C
h , compound 1 was obtained as colorless crystals in 35% yield
Synthesis of Co
2 2 2 5 2
NaIJHL)IJphen) Ĵ0.5C H OHĴH O (6). A mix-
ture of CoCO (0.012 g, 0.01 mmol), H L (0.033 g, 0.033 mmol),
3
6
−1
phen (0.020 g, 0.01 mmol), ethanol (7 mL), and water (1 mL)
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12
was placed in a Teflon-lined reactor (15 mL) and heated at 140
SHELXL-97 program within WINGX. All non-hydrogen atoms
were easily found from the Fourier difference maps and refined
with anisotropic temperature parameters. In the model, hydro-
gen atoms bound to carbon were geometrically located. The
hydrogen atoms attached to carboxylate O atoms in 1, 8 and 9
and one free water molecule in 9 were located from difference
Fourier maps and refined with isotropic displacement parame-
ters. The hydrogen atoms attached to carboxylate O atoms in 6
and hydrogen atoms of one free ethanol molecule in 9 were geo-
metrically located. The disordered atoms in 2, 3, 5 and 6 were
treated using a split-atom model. For 6, the free water molecules
O2W and O3W were, respectively, refined as a disordered atom
using O atom split over two sites with a total occupancy of 0.5.
The hydrogen atoms of the disordered C in 3 and 5, coordi-
nated water molecule in 1, and free water molecules and etha-
nol molecules in 6 and 8 could not be found from difference
Fourier maps. In refinement of compound 1, the SQUEEZE rou-
tine of PLATON was used to remove the seriously disordered
°
C for 3 days. After gradually cooling to room temperature at a
−1
rate of 10 °C h , the pink crystals were obtained in 30% yield
based on CoIJII). Anal. calcd for C H Co NaN O (Mr
=
79
58
2
4 19.5
1
3
1
1
1
8
516.18): C, 62.58; H, 3.86; N, 3.69. Found: C, 62.91; H, 3.93; N,
−1
.62. IR (cm ): 3649(w), 3420(w), 3067(w), 2895(w), 2617(w),
707(m), 1625(m), 1562(s), 1541(s), 1516(m), 1485(m), 1438(s),
397(s), 1374(s), 1314(m), 1281(m), 1226(s), 1141(w), 1102(m),
055(w), 1017(m), 991(m), 907(w), 887(w), 869(w), 843(m),
17(w), 802(m), 763(m), 726(m), 681(m), 641(w), 547(w), 423(w).
Synthesis of Co IJL)IJ4,4′-bpy) (7).
A
mixture of
3
CoIJCH COO) Ĵ4H O (0.025 g, 0.01 mmol), H L (0.033 g, 0.033
3 2 2 6
mmol), 4,4′-bpy (0.016 g, 0.01 mmol), ethanol (6 mL), and
water (2 mL) was placed in a Teflon-lined reactor (15 mL)
and heated at 140 °C for 3 days. After gradually cooling to
room temperature at a rate of 10 °C h , compound 7 was iso-
lated as pink crystals in 36% yield based on CoIJII). Anal. calcd
−
1
for C64
3 2 r
H44Co N O18 (M = 1305.84): C, 58.87; H, 3.39; N, 2.15.
−
1
13
Found: C, 58.42; H, 3.46; N, 2.08. IR (cm ): 3861(w), 3744(w),
solvent molecules. The molecular formula of 1 was calculated
3
1
1
8
674(w), 3592(w), 3522(w), 3444(w), 3072(w), 2969(w),
717(w), 1654(m), 1602(m), 1566(s), 1440(s), 1396(s),
284(m), 1227(m), 1125(w), 1073(w), 1014(m), 935(w), 873(w),
16(w), 767(m), 677(w), 545(w), 457(w).
by the contribution of the removed electrons and further con-
firmed by the thermogravimetric and elemental analytical data.
The topologies of compounds 6–8 were analyzed by using the
14
OLEX program. PLATON calculations show that the void (with-
3
Synthesis of Cu
2
IJH
2
L)IJ4,4′-bpy)
4
Ĵ0.5H
2
O (8). A mixture of
out the free solvent molecules for 1, 6, 8 and 9) is 1529.6 Å per
3
CuIJCH COO) ĴH O (0.020 g, 0.01 mmol), H L (0.033 g, 0.033
unit cell volume (26.0% of the cell volume) for 1, 133.4 Å per
3
2
2
6
3
mmol), 4,4′-bpy (0.016 g, 0.10 mmol), and water (8 mL) was
placed in a Teflon-lined reactor (15 mL) and heated at 170 °C
for 3 days. After gradually cooling to room temperature at a
rate of 10 °C h , compound 8 was obtained as orange crystals
in 36% yield based on CuIJII). Anal. calcd for C94
unit cell volume (8.1% of the cell volume) for 4, 1022.3 Å per
3
unit cell volume (14.2% of the cell volume) for 6, 266.6 Å per
3
unit cell volume (17.4% of the cell volume) for 7, 468.4 Å per
−
1
3
unit cell volume (5.6% of the cell volume) for 8 and 262.9 Å
H
71Cu
2
N
8
O
18.5
per unit cell volume (12.0% of the cell volume) for 9, respec-
tively. The structures of compounds 2, 3 and 5 are non-porous.
The detailed crystallographic data and structure refinement
parameters for compounds 1–9 are summarized in Table 1.
Selected bond distances and angles and hydrogen bond
parameters for these compounds are listed in Tables S1–S9.†
(M = 1735.70): C, 65.05; H, 4.12; N, 6.46. Found: C, 65.37; H,
r
−
1
4.18; N, 6.39. IR (cm ): 3041(w), 2894(w), 1939(w), 1691(m),
1601(m), 1581(m), 1532(m), 1484(m), 1437(m), 1410(s), 1376(m),
1282(m), 1227(s), 1101(m), 1061(m), 1012(m), 991(m), 928(m),
855(w), 806(m), 763(m), 729(m), 681(w), 627(w), 491(w).
2 2 2 2 5 2
Synthesis of Cu IJH L)IJttp) Ĵ2C H OHĴ2H O (9). A mixture
of CuCO (0.013 g, 0.01 mmol), H L (0.033 g, 0.033 mmol), Results and discussion
3
6
ttp (0.032 g, 0.01 mmol), ethanol (7 mL), and water (1 mL)
was placed in a Teflon-lined reactor (15 mL) and heated at
5 2 2 2 2 5 2
Structure of ijMn IJHL) IJH O) ]Ĵ2C H OHĴ4H O (1)
As shown in Fig. 1a, the asymmetric unit of 1 contains two
and a half MnIJII) atoms, one HL anion, one coordination
water molecule, two lattice water molecules, and one ethanol
molecule. Three MnIJII) atoms (Mn1, Mn2 and Mn3) show
similar distorted octahedral coordination spheres. Mn1 is
surrounded by four HL anions, and Mn2 is coordinated by
five HL anions. The octahedral geometry of Mn3 is completed
by four HL anions and one water molecule. Notably, each HL
anion bridges eleven MnIJII) ions (mode I in Scheme 2). In
this way, the HL anions link adjacent MnIJII) atoms into a 2D
layer structure (Fig. 1b).
1
40 °C for 3 days. After gradually cooling to room tempera-
−
1
ture at a rate of 10 °C h , blue crystals of 9 were obtained in
2% yield based on CuIJII). Anal. calcd for C102
M = 1876.91): C, 65.27; H, 4.72; N, 4.48. Found: C, 65.58; H,
4
(
2 6 22
H88Cu N O
r
−
1
4.78; N, 4.41. IR (cm ): 3650(w), 3445(m), 3069(w), 2972(w),
2873(w), 1684(w), 1602(s), 1562(s), 1479(m), 1430(m), 1381(s),
1307(m), 1273(m), 1227(s), 1169(m), 1114(m), 1096(w),
1072(w), 1051(w), 1009(m), 988(m), 928(w), 896(w), 819(w),
798(m), 774(m), 728(w), 687(m), 654(w), 499(w), 413(w).
X-ray crystallography
Structures of Mn
Cd IJL)IJ2,2′-bpy)
3
IJL)IJphen)
(4) and Cd
2
(2), Mn
IJL)IJphen)
3
IJL)IJ2,2′-bpy)
(5)
2
(3),
Crystallographic diffraction data for compounds 1–9 were
recorded on an Oxford Diffraction Gemini R CCD with graphite-
monochromated Mo Kα radiation (λ = 0.71073 Å) at 293 K. All
the structures were solved by the direct method of SHELXS-97
and refined by full-matrix least-squares techniques using the
3
2
3
2
Compounds 2–5 show similar 2D network structures (Fig. S1–S3†).
Therefore, only the description of 2 is given as a representation.
When phen was introduced into the reaction system of 1, a
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Table 1 Crystal data and structure refinements for 1–9
1
2
3
Formula
C H98Mn O
112 5 44
C
78
H
52
O N Mn
18 4 3
74 3 4 18
C H52Mn N O
M
r
2422.64
1498.06
1450.03
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Monoclinic
P2/c
16.7488(9)
12.8214(9)
30.458(2)
90
116.084(4)
90
5874.5(6)
2
Triclinic
Triclinic
P¯1
P¯1
11.4610IJ12)
12.1260IJ14)
13.130(2)
99.683(4)
106.979(3)
99.307(5)
1676.8(4)
1
11.4290(7)
12.3780(8)
12.7660(9)
100.579(5)
107.948(6)
100.603(5)
1632.05IJ19)
1
1.475
743
α (°)
β (°)
γ (°)
V (Å )
3
Z
D
−3
calc (g cm
)
1.370
2494
1.484
767
F(0 0 0)
R
int
0.0756
1.085
0.0830
0.1875
0.0391
1.015
0.0628
0.1663
0.0552
1.145
0.0758
0.1636
2
GOF on F
a
R
1
[I > 2σIJI)]
(all data)
b
wR
2
4
5
6
Formula
C
H52Cd N
74 3 4
O
18
C
H52Cd N O
78 3 4 18
79 2 4 19.5
C H58Co NaN O
M
r
1622.45
Triclinic
P¯1
1670.50
Triclinic
P¯1
1516.18
Monoclinic
P2 /n
14.3700IJ12)
28.431(2)
17.883(2)
90
100.673(5)
90
7179.8(13)
4
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å )
1
11.4063(9)
12.4905(7)
12.9267(9)
101.825(5)
108.484(6)
99.617(5)
1655.3(2)
1
11.4270(9)
12.1650IJ10)
13.2170IJ10)
100.658(7)
107.125(7)
98.125(6)
1687.6(2)
1
3
Z
−3
Dcalc (g cm
)
1.628
1.644
1.403
F(0 0 0)
812
836
3124
R
int
0.0394
1.054
0.0535
0.1300
0.0411
1.029
0.0602
0.1751
0.0720
1.029
0.0613
0.1598
2
GOF on F
a
R
1
[I > 2σIJI)]
(all data)
b
wR
2
7
8
9
Formula
C
64
3 2
H44Co N O
18
94
C H71Cu
N O
2 8 18.5
102 2 6 22
C H88Cu N O
M
r
1305.84
Triclinic
P¯1
10.6720(7)
12.3940(7)
12.5010(7)
75.378(5)
73.453(5)
87.968(5)
1532.50IJ16)
1
1.415
667
1735.70
Monoclinic
C2/c
32.9860IJ17)
17.3230IJ15)
28.3820IJ17)
90
148.758IJ14)
90
1876.91
Triclinic
P¯1
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å )
8.9200(5)
15.5240(8)
15.8610(8)
90.076(4)
95.216(4)
90.973(4)
2186.9(2)
1
3
8411.5(10)
4
1.371
Z
−3
Dcalc (g cm
)
1.425
976
F(0 0 0)
3588
R
int
0.0512
1.018
0.0607
0.1673
0.1273
1.200
0.1593
0.2919
0.0315
1.025
0.0591
0.1620
2
GOF on F
a
R
1
[I > 2σIJI)]
(all data)
b
wR
2
P
P
P
P
a
b
2
o
2 2
2 2 1/2
R
1
=
||F
o
| − |F
c
||/ |F
o
|. wR
2
= { ijwIJF
− F
c
) ]/ wIJF
o
) ]}
.
different 2D layer structure of 2 was achieved. In 2, Mn1 is five-
coordinated by two nitrogen atoms from one phen and three oxy-
gen atoms from three individual L anions in a distorted trigonal
bipyramid geometry (Fig. 2a). Mn2 is coordinated by six oxygen
atoms from six independent L anions in an octahedral coordina-
tion sphere. Mn1, its symmetry-related species, and Mn2 are held
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Each L anion bridges ten MnIJII) ions (mode II in Scheme 2). Fur-
ther, neighboring trinuclear MnIJII) units are linked by the back-
bones of L anions to yield a 2D layer. The phen ligands as termi-
nal ligands are attached on both ends of the trinuclear MnIJII)
units in bidentate chelating coordination modes (Fig. 2b).
Moreover, there exist two types of π–π stacking in 2 (Fig. 2c).
One type of π–π interaction is between two parallel aromatic
rings containing N2 atoms of phen ligands with interplanar sep-
aration being 3.41 Å (centroid–centroid and slippage distances
of 3.86 and 1.82 Å, respectively), while the other one is between
the middle benzene rings and the aromatic rings containing N1
atoms of phen ligands with interplanar separation being 3.59 Å
(centroid–centroid and slippage distances of 4.04 and 1.86 Å,
respectively). The two types of π–π stacking link the neighboring
2D layers into a 3D supramolecular architecture (Fig. 2c).
Compounds 2 and 3 contain similar nitrogen-containing
ligands phen and 2,2′-bpy and show similar 2D layer struc-
tures. But, in 3, the adjacent 2D layers are extended into a 3D
supramolecular architecture by π–π interactions between the
pyridine rings of 2,2′-bpy, with the interplane and intercentre
lengths of 3.50 and 3.77 Å, respectively (Fig. S1†). Moreover,
the structure of compound 4 is essentially isostructural with
3
3
(Fig. S2†). There are small differences between compounds
and 4. Firstly, there is a difference in the coordination
number of metal centers between 3 and 4. In 3, Mn2 is five-
coordinated in a distorted trigonal bipyramid geometry, while
in 4, Cd2 is six-coordinated in a distorted octahedral coordi-
nation environment. Secondly, the H L ligands behave in dif-
6
ferent coordination modes. In 4, the L anion adopts mode III
(
Scheme 2), whereas it adopts mode II in 3.
Structure of Co NaIJHL)IJphen) Ĵ0.5C H OHĴH O (6)
2
2
2
5
2
Single-crystal X-ray diffraction analysis reveals that 6 crystallizes
Fig. 1 (a) View of the coordination environments of MnIJII) ions in 1. (b)
View of the 2D layer of 1 constructed by HL anions and MnIJII) ions.
in the monoclinic space group P2 /n. The asymmetric unit of 6
1
contains two CoIJII) ions, one NaIJI) ion, one HL anion, two phen
ligands, half free ethanol molecule, and one free water mole-
cule. As depicted in Fig. 3a, Co1, Co2 and Na1 show distorted
octahedral coordination geometries. Each CoIJII) ion is ligated by
together through the bridging oxygen atoms from different carbox-
ylate groups of L anions to generate a trinuclear ijMn IJCO ) ] unit.
3 2 6
6
Scheme 2 Coordination modes of the H L in 1–9.
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Fig. 2 (a) View of the coordination environments of MnIJII) ions in 2. (b) View of the 2D layer composed of L anions, phen ligands and MnIJII) ions.
c) View of the 3D supramolecular architecture formed by π–π stacking.
(
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four oxygen atoms from three HL anions and two nitrogen
atoms from one phen ligand. Each NaIJI) ion is surrounded by
four individual HL anions. Co1, Na1 and Co2 are joined
together by the carboxylates from HL anions to result in a
trinuclear ijCo NaIJCO ) IJCOOH)] unit. Adjacent trinuclear
2
2 5
ijCo NaIJCO ) IJCOOH)] units are further extended by the back-
2
2 5
bones of four HL anions in mode IV to yield a 3D framework.
The phen ligands as terminal ligands are located on both ends
of the trinuclear units in bidentate chelating coordination
modes (Fig. 3b).
From a topological point of view, by regarding the trinuclear
unit and the HL anion as 4-connected nodes, respectively, the
overall 3D framework can be rationalized as
a
binodal
2
3
4-connected framework with the point symbol of IJ4 6 8) (Fig. 3c).
2
3
Structure of Co IJL)IJ4,4′-bpy) (7)
In 7, two kinds of CoIJII) ions exhibit different coordination
geometries. As illustrated in Fig. 4a, Co1 is six-coordinated by
six oxygen atoms from six L anions in an octahedral coordina-
tion sphere, whereas Co2 is five-coordinated by four oxygen
atoms from three L anions and one nitrogen atom from one
4,4′-bpy ligand in a distorted trigonal bipyramid geometry. Co1,
Co2 and its symmetry-related species are linked together by the
bridging oxygen atoms from different carboxylate groups to pro-
duce a trinuclear ijCo IJCO ) ] unit. Neighboring trinuclear ijCo -
3
2 6
3
2 6
IJCO ) ] units are connected by the backbones of L anions in
mode V to afford a 2D layer. Adjacent layers are further
extended by 4,4′-bpy ligands into a 3D framework (Fig. 4b).
Topologically, if L anion is considered as a four-connected
node, 4,4′-bpy ligand is simplified as a single linker, and the
trinuclear ijCo IJCO ) ] unit can be viewed as a six-connected
3
2 6
node, the structure of 7 can be described as a 3D (4,6)-
4
2
4 10
connected IJ4 6 )IJ4 6 8) net (Fig. 4c).
Structure of Cu
As shown in Fig. 5a, the asymmetric unit of 8 contains one
crystallographically unique CuIJII) ion, half H L anion, two
,4′-bpy ligands, and a quarter lattice water molecule. Each
2 2 4 2
IJH L)IJ4,4′-bpy) Ĵ0.5H O (8)
2
4
CuIJII) ion is in a tetrahedral geometry, completed by four
nitrogen atoms of four different 4,4′-bpy ligands. As illus-
trated in Fig. 5b, each 4,4′-bpy ligand bridges two CuIJII) ions
with its two nitrogen atoms to furnish a 3D framework with
large open windows. The diameter of the cavities within the
3
D open framework is approximately 13.6 Å. A striking fea-
ture of 8 is that there are two crystallographically indepen-
dent H L anions located inside the channels in parallel posi-
2
tions (mode VI) (Fig. 5c).
From a topological view, if each CuIJII) ion can be consid-
ered as a 4-connected node, and each 4,4′-bpy ligand is
viewed as a linker, the framework of 8 will be a 4-connected
6
net with a Schläfli symbol of 6 (Fig. 5c).
Structure of Cu
2 2 2 2 5 2
IJH L)IJttp) Ĵ2C H OHĴ2H O (9)
The independent unit of 9 consists of one CuIJII) ion, half H
2
L
anion, one ttp ligand, one lattice water molecule, and one
free ethanol molecule. Each CuIJII) ion is five-coordinated by
three nitrogen atoms from one tridentate chelating ttp ligand
Fig. 3 (a) View of the coordination environments of CoIJII) and NaIJI)
ions in 6. (b) View of the 3D framework of 6. (c) View of the 3D
and two carboxylate oxygen atoms from two distinct H2L
2
3
4
-connected IJ4 6 8)
2
topology of 6.
anions, showing a distorted trigonal bipyramid geometry
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2D layers into a 3D supramolecular architecture. In addition,
there exists O10–H10⋯O8 hydrogen-bonding interaction
between ethanol molecule and carboxylate oxygen atom of
the H L anion, which further stabilized the 3D supramolecu-
2
lar architecture of 9 (Fig. 6c).
Coordination modes of the H
From the structure descriptions above, it can be seen that
L adopts various coordination modes in 1–9 owing to the
6
L ligand
H
6
flexible nature of the –O–CH – spacers and the versatile coor-
2
dination modes of carboxylic acids. On the other hand, the
H
6
L ligand can be partly or fully deprotonated to afford the
H L, HL and L anions. As shown in Scheme 2, H L ligands
2
6
display seven coordination modes in compounds 1–9. H
6
L in
1
–9 can bridge four, nine, ten and eleven metals. The differ-
ent coordination modes of H L play an important role in the
6
formation of the resultant structures. For instance, in 1 and
6
1
2
6
, H L ligands are partly deprotonated to form HL anions. In
, each HL anion bridges eleven metals in mode I to yield a
D layer, while in 6 each HL anion coordinates to nine metal
ions (mode IV) to result in a 3D framework. In 2–5 and 7, the
H L ligands are fully deprotonated to form L anions. Each L
6
anion bridges ten metal ions (modes II, III and V), leading to
the 2D sheets of 2–5 and 7. In 8 and 9, each H
6
L ligand is
partly deprotonated to produce a H L anion. In 8, the free
2
H
2
L anions are included in the channels of the 3D framework
composed of 4,4′-bpy ligands and metal ions. In 9, the H
2
L
anions bridge metal ions (mode VII) to generate a 1D chain.
It is particularly noted that the coordination modes I–VII in
1
–9 are entirely different from the ones observed in the two
previously reported complexes ijZn IJL)IJH O) ]Ĵ3DMFĴ7H O
3
2
2
2
5d
(
3 2 2 6 3 2 2 6 2
MOF-1) and ij(CH ) NH ] ijNi IJL) IJH O) ]Ĵ3DMFĴ15H O (MOF-2).
In the reported MOF-1, each carboxylate group of the L anion
bridges two ZnIJII) atoms, whereas each carboxylate group of the
L anion connects one NiIJII) atom in MOF-2. It is evident that the
different coordination fashions of H
on the final structures of the compounds.
6
L show important effects
15,18b
Effect of the N-donor ligands on the structures of the
compounds
It is well known that the N-donor ligands have a significant
1
5c,16
effect on the complex structures.
Compound 1 shows a 2D
layer structure. However, when the different N-donor ligands
were introduced into the reaction system of 1, compounds 2–9
Fig. 4 (a) View of the coordination environments of CoIJII) ions in 7. (b)
View of the 3D framework of 7. (c) View of the (4,6)-connected
IJ4 6 )IJ4 6 8) topology of 7.
4
2
4
10
were obtained. In 6, the HL anions link the trinuclear ijCo Na-
2
IJCO ) IJCOOH)] units to generate a 3D framework, where phen
2
5
ligands attached on both ends of the trinuclear units as termi-
nal ligands. Compared with phen ligands in 6, 4,4′-bpy ligands
in 7 act as linkers. In 7, the L anions bridges the trinuclear ijCo3-
(
Fig. 6a). The H L anions bridge CuIJII) ions in mode VII to
2
yield an infinite 1D chain. The ttp ligands as terminal ligands
are attached on both sides of the chains in tridentate chelat-
ing coordination modes (Fig. 6b). Two adjacent chains are
linked by intermolecular O1W–H1A⋯O2 and O1W–
2 6
IJCO ) ] units to yield the 2D layer, which are further extended
by 4,4′-bpy ligands to give a different 3D framework. Moreover,
compounds 8 and 9 also display distinct structures because of
the introduction of different N-donor ligands. In 8, 4,4′-bpy
ligands connect metal ions to form a 3D porous framework,
#
5
H1B⋯O5
hydrogen-bonding interactions, yielding a 2D
supramolecular layer. Moreover, additional intermolecular
#
4
O6–H6⋯O9 hydrogen-bonding interactions further link the
where the free H L anions are included, while in 9 metal ions
2
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Fig. 5 (a) View of the coordination environment of the CuIJII) ion in 8. (b) View of the 3D framework (left) of 8 constructed by 4,4′-bpy ligands and CuIJII)
6
2
atoms, and schematic representation (right) of the 4-connected framework with 6 topology. (c) Views of the 3D channels occupied by the H L anions.
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ligand 2,2′-bpy. Clearly, the N-donor ligands display a crucial
16a,c
influence on the final structures of the complexes.
Diffuse reflectance spectroscopy
6
The UV-vis diffuse reflectance spectra of the H L ligand and com-
pounds 1–9 were carried out in the solid state at room temperature
(
Fig. 7). The H L ligand exhibits two strong absorption bands cen-
6
tered at 238 and 299 nm, which can be ascribed to n → π* or π →
5c,17
π* transitions.
from 200 to 353 nm in the ultraviolet region, which are dominated
by the absorption of H L ligands. Compounds 6–9, respectively,
Compounds 1–9 exhibit similar broad bands
6
show additional bands with maxima at 534, 560, 460, and 634 nm
in the visible region. These absorption bands are tentatively attrib-
18
uted to the d–d transitions of metal ions as previously reported.
Photoluminescence properties
The solid state photoluminescence properties of compounds
and 5 have been investigated at room temperature (Fig. 8).
4
According to the previous study, the emission spectra of the
free 2,2′-bpy display two peaks at 416 and 543 nm under 341
1
8–20
nm excitation.
Moreover, it is also found that the
Fig. 6 (a) View of the coordination environment of the CuIJII) ion in 9.
(b) View of the 1D chain of compound 9. (c) View of the 3D supramolecular
architecture formed by hydrogen-bonding interactions (H-bonds: green lines).
are linked by H L anions to produce the 1D chain. The ttp
2
ligands are attached on both sides of the 1D chain as terminal
ligands. Compound 2 exhibits a similar structure to 3 because
of the introduction of the similar potential nitrogen containing
6
Fig. 7 UV-vis spectra of H L and compounds 1–9 in the solid state at
room temperature.
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polycrystalline samples at an applied magnetic field of 1000
Oe in the temperature range of 2–300 K (Fig. 11).
3
−1
m
For 1, χ T is 18.81 cm mol K at 300 K, which is slightly
3
−1
small compared to the spin-only value (21.88 cm mol K)
expected for five magnetically isolated high-spin MnIJII) ions
2
4
with g = 2.0. Upon cooling, χ
m
T continuously decreases to
3
−1
reach a minimum of 15.07 cm mol K at 44 K, which is
followed by an abrupt increase and then a final decrease to
reach 3.48 cm mol K at 2 K. The magnetic susceptibility
3
−1
above 44 K conforms to the Curie–Weiss law with C = 19.97
3
−1
cm mol K and Θ = −14.15 K. This plot is typical of the pres-
ence of antiferromagnetic coupling with the occurrence of a
weak spin canting, which would be responsible for the
2
5
increase in χ T at low temperatures.
m
The magnetic behavior of 3 is similar to that of 1. For 3, the
3
−1
χ T value at 300 K (11.00 cm mol K) is slightly lower than the
m
Fig. 8 Emission spectra of compounds 4 and 5.
3
−1
three non-interacting MnIJII) ions (13.13 cm mol K, with S = 1/2
and g = 2.00). Upon cooling, the values of χ T firstly decrease
m
26
emission bands for the free phen and H
6
L in the solid state
are at 380 nm (λex = 325 nm) and 524 nm (λex = 289 nm),
5
d,21
respectively.
The emission bands for the free ligands are
2
2
probably due to π* → n or π* → π transitions. Irradiated by
UV light at ambient temperature, two compounds show emis-
sion bands centered at 428 nm (λex = 330 nm) for 4 and 555
nm with a shoulder at 408 nm (λex = 324 nm) for 5. In order
to further elucidate the origin of the emissions, the solid-
state emission spectra of 4 and 5 were measured by varying
the excitation wavelengths under the same metrical condi-
tions (Fig. 9). The emission band of 4 is centered at 433 nm
with an excitation wavelength at 341 nm, which probably can
be attributed to the 2,2′-bpy fluorescent emission (λex = 416
nm). With the increase in the excitation wavelength, the
emission bands for 4 are almost the same, indicating that
the observed emission for 4 is mainly based on the lumines-
cence of the 2,2′-bpy ligand. Compound 5 shows an emission
band centered at 548 nm with an excitation wavelength at
2
6
89 nm, which probably can be attributed to the H L fluores-
cent emission (λex = 524 nm). Similar to 4, the emission band
for 5 remains nearly constant with an increase in the excita-
tion wavelength. This result indicates that the emission of 5
is primarily from the luminescence of the H L ligand.
6
The luminescence decay curves of compounds 4 and 5 fit
1
8b
well into double-exponential functions, respectively.
results reveal that there are two luminescence centers in each
compound (Fig. 10). The emission decay lifetimes are τ
The
=
1
2
2
2 1
.82 ns and τ = 16.43 ns (χ = 0.997) for 4 and τ = 1.06 ns
and τ = 5.31 ns (χ = 1.005) for 5, respectively. These lumi-
2
2
nescence lifetimes are much shorter than those originating
−
3
from a triplet state (>10 s). Clearly, the emissions for 4–5
7
e
should arise from the singlet state, and their emissions are
2
3
fluorescent in nature.
Magnetic properties
Fig. 9 Solid-state emission spectra of 4 (a) and 5 (b) by varying the
excitation wavelengths from 280 to 330 nm under the same metrical
conditions.
The temperature-dependent magnetic susceptibility data of
compounds 1, 3, and have been measured for
6
7
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Fig. 10 Luminescence decay curves for compounds 4 (a) and 5 (b) (the black circles represent experimental data, and the solid red lines represent
fitting results).
m−
1
Fig. 11 Plots of the temperature dependence of χ
m
T (open triangles) and χ
(open squares) for compounds 1 (a), 3 (b), 6 (c) and 7 (d).
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constantly, next an inflexion at 44 K appears, then reach the
highest value of 17.89 cm mol K at 34 K, and finally fall to the
34 K and below 12 K) suggest the antiferromagnetic exchange
3
−1
28,30
interactions.
The increase in χ T values (34–12 K) can be
m
3
−1
value of 4.63 cm mol K at 2 K. The magnetic susceptibility
attributed to the presence of intramolecular ferromagnetic inter-
3
above 46 K conforms to the Curie–Weiss law with C = 11.68 cm
actions between the CoIJII) ions mediated by the carboxylate brid-
−1
28
mol K and Θ = −13.99 K.
For 6, the χ T value at room temperature is 1.91 cm mol K,
which is comparable to the expected χ T value (1.875 cm
mol K) of one magnetism-isolated CoIJII) ion with S = 3/2
and g = 2.0, indicating a little orbital contribution as also found in
ges. The magnetic susceptibility above 45 K can be well fit to
3
−1
3
−1
m
Curie–Weiss law with C = 6.52 cm mol K and θ = −42.31 K.
3
m
−
1
PXRD patterns and thermal analyses
2
7
many other high-spin CoIJII) complexes. Upon cooling, the
The purity of the bulk samples was confirmed by using PXRD
patterns. As shown in Fig. 12, the experimental PXRD patterns
correspond well to the simulated ones for each compound.
Thermogravimetric analyses (TGA) were measured for
compounds 1–9 in order to examine their thermal stability
(Fig. 13). For 1, the first weight loss of 7.10% between 25 and
99 °C is consistent with the removal of two free ethanol mole-
cules and four lattice water molecules (calcd 6.77%). Decom-
position of the organic framework begins above 324 °C. The
remaining residue is attributed to the formation of MnO2
(obsd 18.12%, calcd 17.95%). The decomposition of the organic
components occurs at 348 °C for 2, 349 °C for 3, 271 °C for 4,
332 °C for 5, and 363 °C for 7, respectively. The remaining
values of χ T keep smoothly decreasing in the 300–2 K range,
m
2
8
indicating an overall antiferromagnetic coupling in complex 6.
The magnetic susceptibility above 50 K can be fit to Curie–Weiss
law with C = 26.15 cm mol K and θ = −132.42 K. The χ T
value for 7 is 5.97 cm mol K at room temperature, which is
3
−1
m
3
−1
3
−1
very close to the theoretic value of 5.625 cm mol K for three
uncoupled CoIJII) ions with a spin value of 3/2 and a g value of
2
9
2
.0. From room temperature, the χ
m
T value gradually decreases
3
−1
to the minimum value of 3.66 cm mol K with cooling to 34 K,
then increases as the temperature is lowered and reaches a maxi-
mum value of 5.14 cm mol K at 12 K. Finally, it decreases to
3
−1
3
−1
3
.99 cm mol K at 2 K. The two decreases in χ T values (above
m
Fig. 12 Simulated (black) and experimental (red) PXRD patterns of 1–9.
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Fig. 13 TGA curves of compounds 1–9.
weight corresponds to the formation of MnO
7.15%, calcd 17.42%) and 3 (obsd 18.35%, calcd 18.00%), CdO
for 4 (obsd 23.41%, calcd 23.74%) and 5 (obsd 22.84%, calcd
3.06%), and Co for 7 (obsd 19.45%, calcd 19.05%). For 6,
2
for 2 (obsd
hexacarboxylate ligand and different N-donor ligands. These
compounds display fascinating 1D, 2D and 3D structures. The
structural diversities of the complexes indicate that the flexible
hexacarboxylate ligand is a good candidate for construction of
coordination polymers with fascinating motifs. The results also
show that N-donor ligands have great effects on the resultant
structural motifs. The magnetic properties for compounds 1, 3
and 6–7 show the presence of antiferromagnetic interactions
among the metal cations. The luminescence properties of com-
pounds 4 and 5 imply that they may be good candidates for
luminescent materials. It is anticipated that other related coor-
dination polymers with various fascinating structures could be
obtained in the future work.
1
2
2 3
O
the weight loss of 3.1% in the temperature range of 30 to 97 °C
is consistent with the removal of half free ethanol molecule and
one free water molecule (calcd 2.70%). The structure decompo-
sition occurs from 318 °C, with CoO and Na CO as the residue
2
3
(obsd 12.88%, calcd 13.38%). The first weight loss correspond-
ing to the release of water molecules are observed before 198 °C
for compound 8 (obsd 0.43%, calcd 0.52%) and 278 °C for 9
(obsd 6.51%, calcd 6.82%). The decomposition of the organic
components occurs at 218 °C for 8 and 299 °C for 9, respec-
tively. The remaining weight may correspond to the formation
of CuO for compounds 8 (obsd 9.43%, calcd 9.16%) and 9 (obsd
8.83%, calcd 8.47%).
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (grant no. 21277022, 21371030,
21301026, and 21471029) and the Fundamental Research
Funds for the Central Universities.
Conclusion
In summary, nine new coordination polymers were successfully
synthesized under hydrothermal conditions by using a flexible
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