Three unprecedented open frameworks based on a pyridyl-carboxylate: Synthesis, structures and properties

Article abstract of DOI:10.1039/c2ce05948g

Three open frameworks, [Ni(pnta)₂]·1.3DMF (1), [Zn ₂(pnta)₃(OH)]·2DMF (2), and [Cd(pnta) ₂]·3.8DMF (3), were obtained by solvothermal reactions between 6-(pyridin-4-yl)nicotinic acid (Hpnta) and nickel(II), zinc(II) and cadmium(II) nitrate, respectively. Compound 1 is a chiral framework with a fourfold interpenetrated diamondoid network structure and two types of chiral channels. Compound 2 also possesses the fourfold interpenetrated adamantanoid architecture with helical rhombic nanotube-like channels, each of which has two sides of double-layer walls and two other sides of single-layer walls. Compound 3 is a rarely reported double-walled framework with bcu topology. The luminescent properties of compounds 2 and 3 have been studied in the solid state at room temperature.

Full text of DOI:10.1039/c2ce05948g

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PAPER
Three unprecedented open frameworks based on a pyridyl-carboxylate:
synthesis, structures and properties†
ab
Shengqun Su, Wan Chen, Xuezhi Song, Min Zhu, Chao Qin, Shuyan Song, Zhiyong Guo,
Song Wang, Zhaoming Hao, Guanghua Li and Hongjie Zhang*
ab
ab
a
a
a
d
ab
ab
c
a
Received 26th July 2011, Accepted 7th December 2011
DOI: 10.1039/c2ce05948g
Three open frameworks, [Ni(pnta)
2 2 3 2
]$1.3DMF (1), [Zn (pnta) (OH)]$2DMF (2), and [Cd(pnta) ]$
3
.8DMF (3), were obtained by solvothermal reactions between 6-(pyridin-4-yl)nicotinic acid (Hpnta)
and nickel(II), zinc(II) and cadmium(II) nitrate, respectively. Compound 1 is a chiral framework with
a fourfold interpenetrated diamondoid network structure and two types of chiral channels. Compound
2
also possesses the fourfold interpenetrated adamantanoid architecture with helical rhombic
nanotube-like channels, each of which has two sides of double-layer walls and two other sides of single-
layer walls. Compound 3 is a rarely reported double-walled framework with bcu topology. The
luminescent properties of compounds 2 and 3 have been studied in the solid state at room temperature.
Introduction
example, have probed into the preparation of novel optical and
magnetic materials by utilizing unsymmetrical pyridyl-carboxy-
6
late and analogous bridging moieties. The presence of varying
The rational design and construction of coordination polymers
based upon assembly of metal ions and multifunctional organic
ligands has drawn widespread attention because of their poten-
tial applications as functional materials and intriguing varieties
of architectures and topologies. However, targeted synthesis of
coordination polymers with the predesigned structure and
functionalities in these ligands confers interesting properties on
the resultant compounds, and the asymmetry of such ligands
7
renders it possible to construct helical motifs. Additionally, both
neutral and anionic donor groups in the ligands can coordinate
to metal ions potentially to form neutral frameworks. The
absence of counterions in such neutral networks increases the
odds of resulting in porous solids.
1,2
desired property is still a formidable challenge. The structures
of coordination polymers are usually influenced by a multitude
of factors such as geometrical and electronic properties of the
metal ions employed, coordination abilities of the ligands, the
With this in mind, we synthesized a bifunctional ligand Hpnta
(
6-(pyridin-4-yl)nicotinic acid) as the organic linker (Scheme 1)
3
ligand-to-metal ratio, and the use of different solvents. Amid
and successfully obtained three novel compounds, [Ni(pnta)
2
]$
]$
them, the careful selection of organic ligands and metal ions
plays a decisive role in the preparation of coordination polymers.
The bulk of research endeavors in this arena have so far been
revolving around coordination polymers with either neutral
1
3
2 3
.3DMF (1), [Zn (pnta) (OH)]$2DMF (2), and [Cd(pnta)
2
.8DMF (3). The crystal structures of these compounds and
topological analyses, along with the investigation of the modu-
lated effect of various metal ions and coordination modes of
ꢀ
4
donor ligands or strictly anionic groups. However, multifunc-
pnta anions on the ultimate structures, will be represented and
tional ligands combining neutral groups with anionic groups
5
have attracted a great deal of interest currently. Lin et al., for
discussed below in detail.
a
State Key Laboratory of Rare Earth Resource Utilizations, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun, 130022, P. R. China. E-mail: hongjie@ciac.jl.cn; Fax: +86
4
31 85698041; Tel: +86 431 85262127
b
Graduate School of the Chinese Academy of Sciences, Beijing, 100039, P.
R. China
c
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,
College of Chemistry, Jilin University, Changchun, 130012, P. R. China
d
Department of Chemistry, University of Texas at San Antonio, One
UTSA Circle, San Antonio, Texas, 78249-0698, USA
†
Electronic supplementary information (ESI) available. CCDC
reference numbers 836983–836985. For ESI and crystallographic data
in CIF or other electronic format see DOI: 10.1039/c2ce05948g
Scheme 1 Synthesis route for ligand.
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ꢀ
monochromatized Mo Ka radiation (l ¼ 0.71073 A). The crystal
Experimental section
structure was solved by means of Direct Methods and refined
Materials and methods
2
9
employing full-matrix least squares on F (SHELXTL-97). All
the hydrogen atoms except for the disordered guest DMF
molecules were generated geometrically and refined isotropically
using the riding model. C3 and C4 atoms in 1 and C35, C37, C41,
C42 and O10 atoms in 2 were refined with isotropic temperature
parameters and other non-hydrogen atoms were refined aniso-
tropically. The restrains of DFIX were applied to keep the
disordered DMF molecules reasonable in compound 2. For
compounds 1 and 3, during the structure refinement, the atoms
of the (DMF) solvent molecule were observed but could not be
modeled satisfactorily. Therefore, the contributions of the
disordered solvent molecules (DMF) were removed from the
diffraction data using the SQUEEZE routine of PLATON
Hpnta (6-(pyridin-4-yl)nicotinic acid) was synthesized as repor-
8
ted in the literature with some modification, and other reagents
were purchased from commercial sources and used as received.
IR spectra were obtained from KBr pellets on a Perkin-Elmer
ꢀ1
5
80B IR spectrometer in the 400–4000 cm region (ESI†).
Elemental analyses (C, H, N) were performed with a VarioEL
analyzer. Thermogravimetric analysis (TGA) was performed on
ꢁ
a Perkin-Elmer TG-7 analyzer heated from 40 to 700 C under
nitrogen. The luminescent properties of compounds were
measured on a HITACHI F-7000 spectrometer. Powder X-ray
diffraction data were collected on a Bruker D8-ADVANCE
ꢁ
ꢀ1
diffractometer equipped with Cu Ka at a scan speed of 2 min .
Nitrogen sorption experiments were carried out on a Quanta-
chrome Autosorb Automated Gas Sorption System. Prior to the
10
software and then final refinements were carried out. Addi-
tionally, the numbers of disordered guest molecules were deter-
mined according to elemental analyses and thermogravimetric
analyses. Crystal data and details of the structure determination
for complexes 1–3 are listed in Table 1.
N
2
isotherm measurements at 77 K, the samples were outgassed
ꢁ
under vacuum at 120 C overnight.
Synthesis
[
Ni(pnta) ]$1.3DMF (1). A mixture of Ni(NO ) $6H O (0.0174
2 3 2 2
g, 0.06 mmol), Hpnta (0.0201 g, 0.1 mmol), triethylamine (TEA)
0.045 ml), DMF (2 ml) and ethanol (1 ml) was stirred for 10 min
Results and discussion
(
ꢁ
and transferred to a Teflon reactor (20 ml) and heated at 105 C
Structural description of 1
for 2 d. After the sample was gradually cooled to room
ꢀ1
Compound 1 crystallizes in the chiral tetragonal space group P42
ꢁ
temperature at a rate of 5 C h , green crystals of 1 were
(
1)2. Note that Flack’s parameter for the crystal is 0.52(2), which
obtained with 38% yield based on Hpnta. Anal. calcd for
means that the chiral framework forms a twinned racemate
crystal. The asymmetric unit of 1 contains one independent Ni
center and two organic ligands. The Ni1 center adopts a distorted
octahedral geometry by coordinating to four oxygen atoms from
C
25.90
H
23.10
N
5.30NiO5.30 (M
r
¼ 552.11): C, 56.34; H, 4.22; N,
ꢀ1
1
3.44%. Found: C, 56.58; H, 3.84; N, 13.39%. IR (cm ): 3240
(
(
m), 2921(m), 1610(s), 1584(s), 1560(s), 1381(m), 1161(w), 1055
w), 1014(w), 834(w), 779(m), 753(m), 534(w), 468(w).
ꢀ
two different pnta ligands (O1, O2, O3A and O4A) and two
ꢀ
nitrogen atoms (N4 and N2B) from two pnta ligands. The Ni–O
6b
and Ni–N bond lengths are all within the normal ranges. The
[
Zn (pnta) (OH)]$2DMF (2). A mixture of Zn(NO ) $6H O
2 3 3 2 2
(
0.0208 g, 0.07 mmol), Hpnta (0.0201 g, 0.1 mmol), TEA (0.045
II
six-coordinated Ni center acts as a pseudo-tetrahedral four-
ml), DMF (2 ml) and ethanol (1 ml) was stirred for 10 min and
ꢁ
II
connected node, which connects to four other Ni centers
transferred to a Teflon reactor (20 ml) and heated at 90 C for
ꢀ
through four pnta ligands, resulting in the formation of a dia-
3
d. After cooling to room temperature, colorless crystals of 2
were obtained with 43% yield based on Hpnta. Anal. calcd for
(M
¼ 891.50): C, 52.54; H, 4.07; N, 12.57%.
Found: C, 52.65; H, 4.15; N, 12.52%. IR (cm ): 3256(m), 2930
mondoid network (Fig. 1a). The separations of the adjacent Ni/
ꢀ
ꢀ
Ni atoms in the adamantanoid cage unit are 12.82 A and 12.87 A.
The long spacers between coordination sites result in large
cavities within the adamantanoid cages. In order to minimize the
big void cavities and stabilize the framework by nature, the
potential voids are effectively filled via mutual interpenetration in
the aligned normal type with four independent equivalent
frameworks along the c-axis, generating a fourfold inter-
penetrated adamantanoid architecture (Fig. 1b).
C
39
H36Zn
2
N
8
O
9
r
ꢀ1
(
(
m), 1617(s), 1601(s), 1577(s), 1397(m), 1169(w), 1071(w), 1022
w), 843(w), 794(m), 770(m), 541(w), 476(w).
[
Cd(pnta) ]$3.8DMF (3). A mixture of Cd(NO ) $4H O
2 3 2 2
(
0.0185 g, 0.06 mmol), Hpnta (0.0201 g, 0.1 mmol), TEA (0.030
ml), DMF (1 ml) and ethanol (0.5 ml) was stirred for 10 min and
ꢁ
Despite the fourfold interpenetration, the structure generates
2
transferred to a Teflon reactor (20 ml) and heated at 90 C for 3d.
ꢀ
1
D square channels of window size ca. 10.99 ꢂ 10.99 A with
After cooling to room temperature, colorless crystals of 3 were
DMF molecules located in channels (measured between opposite
atoms). Interestingly, when viewed along the [001] direction, the
structure presents two kinds of square nanotubelike channels
obtained with 51% yield based on Hpnta. Anal. calcd for
C
33.40
H
40.60CdN7.80
O
7.80 (M
r
¼ 788.54): C, 50.87; H, 5.19; N,
3.85%. Found: C, 50.85; H, 4.97; N, 13.51%. IR (cm ): 3231
m), 1593(s), 1569(s), 1390(m), 1063(w), 1014(w), 835(w), 786(m),
62(m), 631(w), 566(w), 541(w), 468(w).
ꢀ1
1
(
(
Type I and Type II) assembled from two types of helices
(
11
Fig. 2a). The Type I chiral channel contains fourfold right-
7
handed helical chains, while II contains fourfold left-handed
helical chains (Fig. 2b). The effective free volume calculated with
X-Ray crystallography
ꢀ
3
PLATON for the inclusion is 3010 A per unit cell (after free
molecules have been hypothetically removed) corresponding to
47.51% of the cell volume.
The X-ray intensity data for the three compounds were collected
on a Bruker SMART APEX CCD diffractometer with graphite-
1
682 | CrystEngComm, 2012, 14, 1681–1686
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Table 1 Crystal data and structure refinements for complexes 1–3
1
2
3
Formula
C
25.90
552.11
Tetragonal
P42(1)2
185(2)
22.3163(5)
22.3163(5)
12.7222(6)
90.00
6335.9(4)
8
1.112
2192
35 274
6259
0.0598
1.015
0.0470
0.1225
0.52(2)
H
23.10
N5.30NiO5.30
C
891.50
Monoclinic
P21/c
185(2)
6.1802(4)
29.4218(18)
23.3127(14)
95.6630(10)
4218.3(5)
4
1.404
1832
23 187
8320
0.0644
1.062
0.0630
0.2100
39
H
36Zn
2
N
8
O
9
C
788.54
33.40 7.80
H40.60CdN7.80O
Formula weight
Crystal system
Space group
T/K
Monoclinic
P21/c
185(2)
8.1191(5)
18.8297(11)
18.7331(12)
100.5740(10)
2815.3(3)
4
1.722
1496
15 363
5550
ꢀ
a/A
ꢀ
b/A
ꢀ
c/A
b/deg
3
ꢀ
V/A
Z
ꢀ
3
Dcalcd/g cm
F(000)
Data collected
Unique data
R(int)
0.0417
1.030
0.0373
0.1048
2
GOF on F
a
1
R
uR
[I > 2s(I)]
(all data)
b
2
Flack (c)
a
b
|. uR
2
o
2
2
2
2
1
R
1
¼ SkF
o
| ꢀ |F
c
k/S|F
o
2
¼ {S[u(F
ꢀ F
c o
2
) ]/S[u(F ) ]}/ .
ꢀ
ꢀ
pnta ligands at the axial position (Cd–O 2.195(5)–2.466(4) A).
Structural description of 2
ꢀ
Neighboring Cd(II) ions are doubly bridged by two –COO from
ꢀ
X-Ray crystallography reveals that 2 crystallizes in space group
P2 /c and exhibits a 3D open framework with 1D rhombic
pnta ligands to give a centrosymmetric dinuclear Cd (COO)
2
2
1
ꢀ
moiety (Fig. 4a), with the distance of Cd/Cd being 3.837 A.
Each dinuclear unit is further connected to neighboring coun-
channels along the x-axis. The asymmetric unit consists of two
ꢀ
Zn atoms, three pnta ligands and one m
2
-OH. The Zn1 center is
ꢀ
ꢀ
terparts through eight pnta ions to generate a 3D open frame-
coordinated by two oxygen atoms, one pnta ligand (O1) and
work with the rectangular channels along the a-axis (Fig. 4b).
ꢀ
one m
2
-OH (O7), two nitrogen atoms (N4A and N6B) from two
ꢀ
Because the eight pnta linkers link the dinuclear units just along
different pnta ligands. The Zn2 center adopts distorted tetra-
hedral coordination geometry, surrounded by three oxygen
four directions, the channels are double-walled. To the best of
our knowledge, only one example of such double-walled frame-
ꢀ
atoms (O4, O5 and O7) from two pnta anions and one hydroxyl
ꢀ
14
works has been reported to date. The DMF molecules are
trapped in channels. Without guest molecules, the effective free
volume is calculated by PLATON analysis to be 37.72% of the
crystal volume. If the dinuclear units are considered as eight-
connected nodes, the resulting network is of the bcu topology
group, one nitrogen atom (N2C) from a pnta ligand. The Zn1
and Zn2 centers are linked by one m -OH to form Zn units. Each
2
2
ꢀ
unit is connected to four others through six pnta ligands in
a tetrahedral fashion, which gives rise to a diamondoid network
composed of large adamantanoid cages. In consequence of
mother nature’s horror vacui, such a structure with extra-large
24
4
with the Schl €a fli symbol of (4 $6 ) (Fig. 4c).
Compounds 1–3 are synthesized under similar conditions
using the same organic ligands with different metal ions. They
have different structures, that is, the chiral fourfold inter-
penetrated adamantanoid architecture, fourfold interpenetrated
diamondoid net and double-walled framework, respectively. It
can be discerned that the central metal ions may play a dominant
role in the construction of the resulting complexes because
different metal ions have varied coordination configurations,
metal radii and coordination spheres. In addition, the coordi-
12
pores is unstable. In this case, four identical diamondoid
networks are filled via mutual interpenetration forming a four-
fold interpenetrated framework. It is noteworthy that there are
still sizable voids in spite of interpenetration. As shown in
Fig. 3b, two types of helical nanotubelike channels (Type I and
Type II) are also visible along the [100] direction (Fig. 3b). Each
of the two channels has two sides of double-layer walls and two
other sides of single-layer walls, which is different from the
13
channels in complex 1. The two channels contain 4-fold right-
handed and left-handed helical chains respectively and hold the
same channel size. PLATON analysis showed that the effective
free volume of 2 is 36.22% of the crystal volume.
ꢀ
nation modes of the pyridyl-carboxylate ligand pnta for
complexes 1–3 are also diverse. The carboxylates of the ligands in
compounds 1–3 adopt chelating-mono (I), mono (II) and bis-
chelating (III)/mono coordination modes, respectively (Fig. 5).
So different coordination modes of the ligand also exert some
influence on the structures of the compounds.
Structural description of 3
X-Ray crystallographic analysis indicates that, in the asymmetric
ꢀ
unit of 3, there are one Cd(II) atom and two pnta ligands. The
Thermal analysis
central Cd(II) ion adopts a distorted octahedral geometry sur-
ꢀ
rounded by four oxygen atoms from two different pnta ligands
In order to characterize the thermal stabilities of compounds 1–3,
in the equatorial plane and two nitrogen atoms from another two
their thermal behaviors were investigated by TGA under
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Fig. 3 (a) Coordination environments of the Zn(II) ions (left) and
a single adamantanoid cage (right) in 2. Hydrogen atoms are omitted for
clarity. Symmetry codes: (A) ꢀx, ꢀy, ꢀz + 1; (B) ꢀx, ꢀy, ꢀz; (C) ꢀx + 2,
y ꢀ 1/2, ꢀz + 1/2. (b) Perspective view along the [100] axis showing two
types of helical channels with fourfold left- and right-hand helical chains,
respectively.
ꢁ
ꢀ1
a nitrogen atmosphere with a heating rate of 10 C min
Fig. S1†). The TGA curve of 1 shows that the weight loss in the
(
ꢁ
Fig. 1 (a) A single diamondoid network structure and coordination
environments of the Ni(II) ions in 1. Hydrogen atoms are omitted for
clarity. Symmetry codes: (A) ꢀx + 1/2, y + 1/2, ꢀz + 1; (B) x ꢀ 1/2, ꢀy +
temperature range of 40–220 C corresponds to the loss of one
free DMF molecule (obsd 13.22%, calcd 13.79%). The decom-
ꢁ
position of the compound occurs at ca. 325 C. The remaining
3
/2, ꢀz. (b) Interpenetration of four independent diamondoid nets in 1.
weight is assigned to the formation of NiO (obsd 13.21%, calcd
1
3
3.53%). Compound 2 lost its DMF molecules between 40 and
ꢁ
70 C (obsd 16.10%, calcd 16.40%). Likewise, the formation of
ZnO (obsd 18.26%, calcd 18.76%) is responsible for the residual
weight of the final solids. For compound 3, the weight loss
attributed to the release of one and a half guest DMF molecule is
ꢁ
observed from 40 to 350 C (obsd 14.82%, calcd 13.89%). The
ꢁ
framework begins to decompose at 370 C.
Photoluminescence properties
10
Luminescent properties of compounds with d metal centers
have been attracting mounting interest owing to their potential
applications in chemical sensors, photochemistry, and electro-
luminescent displays. The luminescence properties of compounds
2
and 3 as well as free Hpnta ligand were studied in the solid state
at room temperature (Fig. 6). Upon excitation at 370 nm,
compound 2 exhibits strong fluorescent emission bands at 422
and 441 nm. Compound 3 shows a main peak at 451 nm with two
shoulders at 422 and 518 nm upon excitation at 380 nm. These
Fig. 2 (a) Perspective view along the [001] axis showing Type I and Type
II helical 1D square channels. (b) Type I and II channels containing
fourfold right- and left-hand helical chains, respectively.
1
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ꢀ
Fig. 5 The coordination modes of ptna ligands in compounds 1–3.
Fig. 6 Emission spectra of ligand and compounds 2 and 3 in the solid
state at room temperature.
Gas sorption property
To examine permanent porosity, methanol-exchanged
ꢁ
compound 2 was activated at a temperature of 120 C under
vacuum overnight for gas sorption studies. As revealed in its
PXRD (Fig. S5†), the activated compound 2 still has a crystalline
form. The nitrogen sorption isotherm at 77 K (Fig. 7) shows type
I sorption behavior with a limited adsorption capacity, which is
Fig. 4 (a) Coordination environments of the Cd(II) ions in 3. (b)
Perspective views of the double-walled framework with nanotube-like
channels in 3. (c) The bcu topological network with Cd
2
clusters as nodes.
emissions are neither metal-to-ligand charge transfer (MLCT)
2+
nor ligand-to-metal transfer (LMCT) in nature since the Zn or
2+
10
Cd ions with d configuration are difficult to oxidize or reduce.
Rather, they can probably be assigned to intraligand (n–p*)
fluorescent emission because almost similar emissions are
Fig. 7
ꢁ
2
N adsorption isotherm (77 K) of compound 2 activated at
120 C (red and blue curves represent adsorption and desorption,
respectively).
15
observed for the free Hpnta at 421 nm and 453 nm.
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significantly low for such a highly porous crystal structure.
Obviously, the pores in activated compound 2 have not been
fully expanded in 1 atm of nitrogen, and the nitrogen adsorption
is not saturated. The nitrogen sorption displays hysteretic sorp-
tion behavior owing to the dynamic feature of the inter-
X. Wei, D. J. Wang and S. L. Qiu, Cryst. Growth Des., 2007, 7,
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penetrating frameworks.
Conclusions
2
011, 13, 2457.
Three unprecedented open frameworks have been successfully
synthesized under solvothermal conditions by reacting Hnpta
with Ni(II), Zn(II) and Cd(II) ions. They exhibit intriguing
structures with the chiral fourfold interpenetrated adamantanoid
architecture, fourfold interpenetrated diamondoid net and
double-walled framework, respectively. The structural diversifi-
cation of compounds illustrates that the different coordination
environments around central metal ions and the diverse coordi-
nation modes of the organic ligands play an important role in the
construction of frameworks. It is believed that the preliminary
results about the effects of different metal ions on structures are
instrumental in the rational design and synthesis of frameworks
with specific structural motifs.
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Acknowledgements
The authors are grateful for financial aid from the National
Natural Science Foundation of China (grant no. 20631040 and
2
0771099) and the MOST of China (grant no. 2006CB601103
and 2006DFA42610).
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