Seven novel coordination polymers constructed by rigid 4-(4-carboxyphenyl)- terpyridine ligands: Synthesis, structural diversity, luminescence and magnetic properties

Article abstract of DOI:10.1039/c3dt52500g

Seven coordination polymers, namely [Mn(4-cptpy)₂]_n (1), [Co(4-cptpy)₂]_n (2), [Mn₃(4-cptpy) ₆(H₂O)]_n·2nH₂O (3), [Co(4-cptpy)(HCOO)(H₂O)]_n·nDMF (4), [Zn ₂(4-Hcptpy)₂Cl₄]_n·2nC ₂H₅OH·nH₂O (5), [Co₄(3-cptpy) ₄(HCOO)₄(H₂O)₂]_n (6), and [Mn(3-cptpy)₂]_n (7) (4-Hcptpy = 4-(4-carboxyphenyl)-4, 2′:6′,4″-terpyridine; 3-Hcptpy = 4-(4-carboxyphenyl)-3, 2′:6′,3″-terpyridine), have been synthesized under hydro(solvo)thermal conditions and structurally characterized. A general solvothermal method is proposed for preparing carboxylate complexes in DMF solution without any basic additive. 1 and 2 possess isostructural 3D metal-organic frameworks containing nanosized cavities. 3 is a beautiful 2D coordination polymer assembled by flower-like Mn₃(4-cptpy) ₆(H₂O) subunits. 4 and 6 both display 2D polymeric networks constructed from 4/3-cptpy^- ligands, in which the formate ligands originate from the hydrolysis of DMF. 5 is a 1D 2₁ helical chain polymer. 7 shows a 2D network with a (3.6) two-nodal kgd topology. 4/3-Hcptpy ligands display seven types of coordination modes. The zinc complex 5 emits strong violet luminescence. 1 and 2 are both thermally stable below 440°C and exhibit antiferromagnetic interactions. The Royal Society of Chemistry 2014.

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DOI: 10.1039/C3DT52500G
Graphical Abstract
Peng Yang, Meng-Si Wang, Jin-Jin Shen, Ming-Xing Li,* Zhao-Xi Wang, Min Shao, Xiang He*
Seven novel coordination polymers constructed by rigid 4-(4-carboxyphenyl)-terpyridine ligands:
synthesis, structural diversity, luminescence and magnetic property
Seven 1D to 3D coordination polymers based on 4/3-Hcptpy ligands were hydro(solvo)thermally
synthesized and structurally characterized. The 4/3-Hcptpy ligands display seven types of
coordination modes. [Mn(4-cptpy)2]n (1) and [Co(4-cptpy)2]n (2) are 3D MOFs containing
nanosized cavities. [Mn3(4-cptpy)6(H2O)]n·2nH2O (3) possesses a beautiful 2D network assembled
by flower-like Mn3(4-cptpy)6(H2O) subunits. The complexse 1 and 2 are thermally stable under
440 °C and exhibit antiferromagnetic interactions.

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ARTICLE TYPE
www.rsc.org/xxxxxx | XXXXXXXX
Seven novel coordination polymers constructed by rigid 4-(4-carboxyphenyl)-
terpyridine ligands: synthesis, structural diversity, luminescence and magnetic
property
5
Peng Yang,a Meng-Si Wang,a Jin-Jin Shen,a Ming-Xing Li,*a Zhao-Xi Wang,a Min Shaob and Xiang He*a
a Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, P. R. China
b Laboratory for Microstructures, Shanghai University, Shanghai 200444, P. R. China
* Corresponding author. E-mail: mx_li@mail.shu.edu.cn, hxiang@shu.edu.cn
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
10 First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
Seven coordination polymers, namely [Mn(4-cptpy)2]n (1), [Co(4-cptpy)2]n (2), [Mn3(4-cptpy)6(H2O)]n·2nH2O (3), [Co(4-
cptpy)(HCOO)(H2O)]n·nDMF (4), [Zn2(4-Hcptpy)2Cl4]n·2nC2H5OH·nH2O (5), [Co4(3-cptpy)4(HCOO)4(H2O)2]n (6), and
[Mn(3-cptpy)2]n (7) (4-Hcptpy = 4-(4-carboxyphenyl)-4,2′:6′,4′′-terpyridine; 3-Hcptpy = 4-(4-carboxyphenyl)-3,2′:6′,3′′-
15 terpyridine), have been synthesized under hydro(solvo)thermal conditions and structurally characterized. A generally
solvothermal method is proposed for preparing carboxylate complexes in DMF solution without any basal additive. 1 and 2
possess isostructural 3D metal–organic frameworks containing nanosized cavities. 3 is a beautiful 2D coordination polymer
assembled by flower-like Mn3(4-cptpy)6(H2O) subunits. 4 and 6 both display 2D polymeric networks constructed from 4/3-
cptpy− ligands, in which the formate ligands originate from the hydrolyzation of DMF. 5 is a 1D 21 helical chain polymer. 7
20 shows a 2D network with a (3.6) two-nodal kgd topology. 4/3-Hcptpy ligands display seven types of coordination modes.
Zinc complex 5 emits strong violet luminescence. 1 and 2 are both thermally stable under 440 °C and exhibit
antiferromagnetic interactions.
application in constructing MOFs.5 As
a series of
Introduction
terpyridine derivatives, carboxyphenyl group substituted
terpyridine ligands have been received heavy attention for
50 good reasons: a) Advantages of rigid backbone and
directional extending ability, which are beneficial to build
up porous frameworks possessing good adsorption capacity.
b) The extended networks with novel topologies can be
constructed based on carboxyphenyl-terpyridine ligands. c)
55 Through multidentate-bridging coordination modes, the
introduction of carboxyl group to terpyridine strengthens
the capability to assemble diverse discrete metallic
polynuclear clusters with potential magnetic interactions. d)
With the help of the natural large π-conjugated structures of
60 the carboxyphenyl-terpyridines, materials with active
photoluminescence properties could be synthesized. e) The
existence of inherent multi-aromatic rings is apt to give rise
to π–π stacking interactions, which will play an important
role in the formation of supramolecular architectures.
25 Over the past decade, coordination polymers and metal–
organic frameworks (MOFs) have attracted intense interest
owing to their intriguing structural motifs and potential
applications as functional materials.1 Much effort has been
focused on the purposeful design and controllable synthesis
30 of coordination polymers employing multidentate ligands
such as polycarboxylate and N-heterocyclic ligands.2
Nevertheless, it is still difficult to direct self-assembly
process and harvest the desired complexes with objective
structures and properties, because many factors can greatly
35 affect the final results, such as the ligand character, metal
coordination geometry, reagent ratio, solvent system, pH
value, reaction temperature and crystallization method.3
Therefore, it is imperative to further investigate the
coordination modes of important multidentate ligands and
40 understand the structure-property relationship inside
coordination polymers.
65
In contrast to the cohesive terpyridyl moiety of 4-(4-
carboxyphenyl)-2,2′:6′,2′′-terpyridine (2-Hcptpy) that often
acts as a chelating group to assemble complexes with
obvious luminescence properties,6,7 4-Hcptpy and 3-Hcptpy
(Scheme 1) contain two side exo-pyridyl groups and trend
Considering as the most popular ligand in this realm,
4,4′-bipyridine has already been used to construct thousands
of complexes.4 Moreover, multipyridyl ligands, such as
45 terpyridine and 2,4,6-tris(4-pyridyl)-1,3,5-triazine, are a
well-known class of ligands and have found widespread
70 to construct extended high-dimensional coordination
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polymers. However, very few efforts were devoted to 4/3-
Hcptpy. Anal. Calcd for C44H28N6O4Co: C, 69.20; H, 3.70;
N, 11.00. Found: C, 69.65; H, 4.12; N, 10.58. IR (KBr,
cm−1): 3442m, 3072w, 3026w, 1594s, 1563s, 1410s,
1312w, 1063w, 1018m, 859w, 824m, 783s, 695m, 478w.
Hcptpy complexes to date.8
Overall, the rigid trigonal 4/3-Hcptpy bifunctional
ligands possess three pyridyl groups and one carboxylic
5
group, which are valuable multidentate ligands in 55 Synthesis of [Mn3(4-cptpy)6(H2O)]n·2nH2O (3). A
constructing coordination polymers and porous MOFs. In
this paper, seven 4/3-Hcptpy coordination polymers were
successfully prepared, in which the 4/3-Hcptpy ligands
exhibit versatile coordination modes. The dimensionalities
mixture of MnCl2·4H2O (19.8 mg, 0.1 mmol), 4-Hcptpy
(35.4 mg, 0.1 mmol) and 8 mL H2O was stirred for 30 min.
Then 0.5 mL NaOH solution (0.1 mol·L−1) was added.
After stirring for another 30 min, the mixture was sealed in
10 of the entire architectures of the seven complexes vary from 60 a 15 mL Teflon-lined reactor. The reactor was heated at
1D to 3D. Herein, we report their syntheses, crystal
structures, thermal stabilities, luminescences, and magnetic
properties.
160 °C for 72 h, and then cooled to room temperature at a
rate of 10 °C h−1. Several yellow crystals of 3 were
separated manually from a mixture of white precipitate.
Anal. Calcd for C132H90N18O15Mn3: C, 67.95; H, 3.89; N,
65 10.81. Found: C, 67.87; H, 4.73; N, 11.17. IR (KBr, cm−1):
3419m, 3063w, 1596s, 1550s, 1399s, 1354m, 1065w,
1016m, 861m, 826s, 786s, 695m, 632m, 479w.
Scheme 1. Schematic description of 4/3-Hcptpy ligands
15
Synthesis of [Co(4-cptpy)(HCOO)(H2O)]n·nDMF (4).
A mixture of Co(NO3)2·6H2O (29.1 mg, 0.1 mmol), 4-
70 Hcptpy (35.3 mg, 0.1 mmol) and 8 mL DMF was sealed in
a 15 mL Teflon-lined reactor. The reactor was heated at
85 °C for 72 h. The red crystals of 4 were collected in 37%
yield based on 4-Hcptpy. Anal. Calcd for C26H24N4O6Co: C,
57.05; H, 4.42; N, 10.24. Found: C, 58.57; H, 4.60; N, 9.14.
75 IR (KBr, cm−1): 3418m, 3068w, 2931w, 1662s, 1596s,
1547s, 1390s, 1065w, 1017w, 830m, 787s, 697m, 632m.
Synthesis of [Zn2(4-Hcptpy)2Cl4]n·2nC2H5OH·nH2O
(5). A mixture of ZnCl2·6H2O (24.4 mg, 0.1 mmol), 4-
Hcptpy (35.3 mg, 0.1 mmol) and 10 mL ethanol was sealed
80 in a 15 mL Teflon-lined reactor. The reactor was heated at
140 °C for 72 h. The light yellow crystals of 5 were
collected in 41% yield based on 4-Hcptpy. Anal. Calcd for
C48H44Cl4N6O7Zn2: C, 52.92; H, 4.07; N, 7.71. Found: C,
53.38; H, 3.60; N, 7.66. IR (KBr, cm−1): 3507m, 3067w,
85 2966w, 2871w, 1684s, 1616s, 1602s, 1539m, 1397s, 1299s,
1217m, 1066s, 1027m, 844s, 774m, 699m, 516m.
20
Experimental section
Materials and methods. Reagents and solvents as well as
4/3-Hcptpy ligands employed were commercially available
25 and used as received. Elemental analyses for C, H and N
were carried out on a Vario EL III elemental analyzer. IR
spectra (KBr pellets) were recorded with a Nicolet A370
FT-IR spectrometer. Thermal analyses were performed on
a Netzsch STA 449C thermal analyzer from 20 to 800 °C
30 in N2 atmosphere. The luminescence spectrum of
crystalline sample was recorded on a Shimadzu RF-5301
PC spectrophotometer. Variable-temperature magnetic
susceptibilities were measured on a Quantum Design
PPMS-9T magnetometer in 2−300 K at a magnetic field of
35 1000 Oe. The diamagnetic corrections were applied by
using Pascal’s constants.
Synthesis of [Co4(3-cptpy)4(HCOO)4(H2O)2]n (6). A
mixture of Co(NO3)2·6H2O (58.2 mg, 0.2 mmol), 3-Hcptpy
(17.6 mg, 0.05 mmol), 3 mL DMF and 3 mL H2O was
90 sealed in a 15 mL Teflon-lined reactor. The reactor was
heated at 120 °C for 72 h. The red crystals of 6 were
collected in 46% yield based on 3-Hcptpy. Anal. Calcd for
C92H64N12O18Co4: C, 59.37; H, 3.47; N, 9.03. Found: C,
58.60; H, 3.45; N, 8.79. IR (KBr, cm−1): 3437m, 3066w,
95 2800w, 1622vs, 1572s, 1389vs, 1353s, 1194m, 1031m,
804s, 784s, 736s, 702s.
Synthesis of [Mn(4-cptpy)2]n (1). MnSO4·H2O (33.8 mg,
0.2 mmol) was added into a 5 mL H2O solution containing
4-Hcptpy (35.3 mg, 0.1 mmol) and 1 mL NaOH solution
40 (0.1 mol·L−1). The mixture was sealed in a 15 mL Teflon-
lined reactor and then heated at 160 °C for 72 h. The yellow
crystals of 1 were obtained in 33% yield based on 4-Hcptpy.
Anal. Calcd for C44H28N6O4Mn: C, 69.57; H, 3.72; N, 11.06.
Found: C, 69.04; H, 4.05; N, 11.28. IR (KBr, cm−1): 3429m,
45 3072w, 3029w, 1594s, 1565s, 1411s, 1314w, 1215w, 1063w,
1016m, 858w, 825m, 784s, 694m, 632m, 476w.
Synthesis of [Mn(3-cptpy)2]n (7). A mixture of
MnSO4·H2O (33.8 mg, 0.2 mmol), 3-Hcptpy (35.3 mg, 0.1
mmol), 3 mL dimethylacetamide (DMA) and 3 mL H2O
100 was sealed in a 15 mL Teflon-lined reactor. The reactor
was heated at 120 °C for 72 h. The light yellow crystals of
Synthesis of [Co(4-cptpy)2]n (2). The preparation
procedure was similar to 1 except that MnSO4·H2O was
replaced by CoSO4·7H2O (56.2 mg, 0.2 mmol). The purple
50 crystals of 2 were obtained in 38% yield based on 4-
2
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7 were obtained in 48% yield based on 3-Hcptpy. Anal.
Calcd for C44H28N6O4Mn: C, 69.56; H, 3.72; N, 11.06.
Found: C, 68.84; H, 3.07; N, 11.06. IR (KBr, cm−1): 3076w,
1626s, 1570s, 1436m, 1379s, 1164s, 1064m, 1033w, 776s,
732m, 716m.
X-ray crystallography. The single crystals of 1−7 were
selected for X-ray diffraction study. Data collections were
performed on a Bruker Smart Apex-II CCD diffractometer
with graphite-monochromatic Mo Kα radiation (λ =
ligands link Mn(II) ions to assemble a 1D necklace-like
polymeric chain with Mn2 dimers as nodes. This 1D chain
is comprised of hexagonal rings with the dimensions of
25.89 Å × 16.25 Å (Mn···Mn distance) in series. With
55 further insight into this structure, it is important to note that
mutual parallel 1D chains do not exist in isolation.
Specifically, adjacent 1D chains interweave with each
other in vertical direction via sharing the metal sites (Fig.
1c). Due to the effective propping originating from the
60 rigid skeleton of 4-cptpy− ligands, complex 1 possesses a
complicated 3D metal–organic framework that contains
nanosized cavities with the dimensions of 16.14 × 16.86 ×
9.69 Å3 (Mn···Mn distance) (Fig. 1d). A more detailed
structural analysis indicates that two identical 3D
65 frameworks interpenetrate with each other to give rise to a
2-fold entangled architecture (Fig. S2, ESI). The potential
solvent-accessible occupancy volume is 5.5% calculated
by PLATON.
5
10 0.71073 Å) at 293(2)
K except 3 at 193(2) K.
Determinations of the crystal system, orientation matrix,
and cell dimensions were performed according to the
established procedures. Lorentz polarization and
absorption correction were applied. The structures were
15 solved by the direct methods and refined by full matrix
least-squares on F2 with the SHELXTL-97 program.9 All
non-hydrogen atoms were refined anisotropically, and
hydrogen atoms were located and included at their
calculated positions. The crystal data and structural
20 refinement results are summarized in Table 1. The selected
bond distances and angles are listed in Table S1
(Electronic supplementary information, ESI). The
measured and simulated powder X-ray diffraction patterns
are shown in Fig. S1 (ESI).
The cobalt complex 2 is isostructural with 1. Both
70 complexes have the similar 3D metal–organic framework.
Recently, Wen et al. reported a [Cd(4-cptpy)2]n·2nDMF
complex, which is a 2D porous MOF and exhibits selective
adsorption of CO2 and luminescence.8a
75 (a)
25
Results and discussion
Description of the structures
Structures of [Mn(4-cptpy)2]n (1) and [Co(4-cptpy)2]n
(2). The X-ray structural analysis reveals that complex 1
30 features a 3D metal–organic framework. As shown in Fig.
1a, the asymmetric unit consists of one independent Mn(II)
ion and two 4-cptpy− ligands. Mn1 is six-coordinated with
a slight distorted octahedral geometry. Four coordination
sites on the equatorial plane are occupied by carboxyl O
35 atoms. The axial positions are occupied by two pyridyl N
atoms with a N4–Mn1–N1 bond angle of 174.25(11)°.
Both independent 4-cptpy− ligands are tridentate and
exhibit different coordination modes. The μ2-cptpy− ligand
coordinates to two Mn(II) ions via a chelating carboxyl
40 group (O3, O4) and an outer pyridyl group (N4) (mode I,
Scheme 2). The μ3-cptpy− ligand combines with three
Mn(II) ions through a bridging carboxyl group (O1, O2)
and an outer pyridyl group (N1) (mode II, Scheme 2). In
each 4-cptpy– ligand, four aromatic rings are essentially
45 coplanar. The central pyridyl group and one remaining
outer pyridyl group are uncoordinated in order to relieve
the steric effect.
80
(b)
85
(c)
(d)
90
95
Fig. 1 (a) The asymmetric unit of 1; (b) the 1D necklace-
like chain with Mn2 dimers; (c) the catena structure; (d)
view of the 3D MOF containing nanosized cavities.
Structure of [Mn3(4-cptpy)6(H2O)]n·2nH2O (3).
Complex 3 is a 2D reticular coordination polymer
It is observed that a Mn2 dimer is formed as a subunit
(Fig. 1b), with the help of the bridging carboxyl group (O1,
50 O2), to build up the framework of 1. The μ2-, μ3-cptpy−
100
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constructed from trinuclear Mn(II) clusters. As illustrated
in Fig. 2a, the asymmetric unit contains three independent
Mn(II) ions, six 4-cptpy− ligands, one coordinated water
trigonal shape in general.10 The linear carboxylate-bridged
Mn3 cluster is still rarely reported.11 A more interesting
observation is that ten 4-cptpy− ligands around every Mn3
and two lattice water molecules. Interestingly, six carboxyl 45 cluster piece together a beautiful flower-like pattern (Fig.
5
groups tightly bind three Mn(II) ions to form a linear Mn3
cluster that acts as a second building unit for constructing
the whole structure of 3 (Fig. 2b). A closer observation
reveals that Mn1 and Mn3 both adopt slight distorted
2c), where Mn3 cluster is taken as a pistil and 4-cptpy−
ligands serve as petals. Among these ten ‘petals’, two 4-
cptpy− anions are terminal ligands, whereas the other eight
ones act as bridging ligands. As shown in Figure 2d,
octahedral geometries. The former is surrounded by two 50 neighbouring Mn3 clusters as subunits are further
10 pyridyl nitrogens, three carboxyl oxygens and water O1W
to complete a distorted cis-octahedral geometry, while the
six coordination sites of Mn3 are all occupied by carboxyl
oxygens from six distinct 4-cptpy− ligands. The whole
interconnected by 4-cptpy− bridging ligands to produce a
2D polymeric network containing flower-like (or starfish-
like)12 motifs, in which the shortest distance between the
Mn3 clusters is 16.832 Å (Mn3···Mn3 distance). Such
Mn3–O bond distances range from 2.105(5) to 2.380(5) Å. 55 structure is rarely observed before.
15 Mn2 is five-coordinated with a distorted triangular-
bipyramidal geometry. The axial positions are occupied by
carboxyl O7 and pyridyl N8 with a O7–Mn2–N8 bond
angle of 175.4(2)°.
(a)
Six independent 4-cptpy– ligands display two types of
20 coordination modes, tridentate mode II and bidentate mode
III (Scheme 2). Each of four tridentate 4-cptpy– ligands
connects three Mn(II) ions via bridging carboxyl group and
an outer pyridyl N atom, while each of two bidentate 4-
cptpy– ligands connects two Mn(II) ions through one
25 bridging oxygen atom from carboxyl group. On the other
hand, six 4-cptpy− ligands could be further divided into
three types owing to the different dihedral angles between
the phenyl ring and the central pyridyl group (Fig. S3, ESI):
a) To reduce the steric hindrance, the dihedral angles of the
30 two 4-cptpy− ligands with central pyridyl N7 and N13 are
nearly the same (exhibiting 43.1° and 45.7°, respectively);
b) Corresponding dihedral angles in another two 4-cptpy
ligands (central pyridyl N1 and N16) range from 20.3° to
60
65
70
(b)
25.5°; c) Regarding to the remaining two 4-cptpy− ligands 75 (c)
35 with three free pyridyl groups, four aromatic rings are
essential coplanar.
It should be noticed that four bidentate-bridging
carboxyl groups and two carboxyl oxygen atoms (O3, O7)
fasten Mn1, Mn2 and Mn3 to aggregate a linear trinuclear
40 {Mn3(μ1,3-CO2)4(μ1,1-CO2)2} cluster. As far as we know,
the analogous {Mn3O(CO2)6} clusters trend to perform
80
(d)
85
90
4
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Page 6 of 13
Fig. 2 (a) The asymmetric unit of 3; (b) the linear carboxylate-bridged Mn3 cluster; (c) the flower-like pattern of 3; (d) the
2D polymeric network.
5
Structure of [Co(4-cptpy)(HCOO)(H2O)]n·nDMF (4).
The asymmetric unit of 4 consists of one independent
Co(II) ion, one 4-cptpy− ligand, one formate ligand, one
coordinated water and one lattice DMF molecule (Fig. 3a).
It should be noticed that the monodenate HCOO– ligand
(c)
55
10 originates from the decomposition of DMF at solvothermal
conditions.13 Co1 adopts
distorted cis-octahedral
geometry, coordinated by four oxygen atoms and two
nitrogen atoms. The chelating carboxyl group (O3, O4) 60 Fig. 3 (a) The asymmetric unit of 4; (b) the 2D hexagonal
a
and two pyridyl N atoms (N1, N3) locate at the equatorial
15 plane. The formate O1 and water O1W atoms occupy the
axial positions with a O1–Co1–O1W bond angle of
176.9(2)º. As a rigid triangular connector, each 4-cptpy−
honeycomb microporous network along bc plane; (c) the 2-
fold interpenetrating layer.
Structure of [Zn2(4-Hcptpy)2Cl4]n·2nC2H5OH·nH2O
(5). Complex 5 possesses a 1D infinite helical chain
ligand combines with three Co(II) ions via the chelating 65 structure. The asymmetric unit is comprised of two
carboxyl group and two outer pyridyl groups (mode IV,
20 Scheme 2) to construct a 2D porous network.
As shown in Fig. 3b, 4-cptpy− ligands serve as three-
connected spacers, and Co(II) ions serve as three-
independent Zn(II) ions, two 4-Hcptpy ligands, four Cl−
ligands, two lattice ethanol molecules and one lattice water
molecule. As shown in Fig. 4a, both Zn(II) ions are
surrounded by two Cl– ions and two pyridyl N donors,
connected nodes, to generate a hexagonal honeycomb 70 exhibiting similar distorted tetrahedral geometries. The
microporous network. The approximate dimensions of the
25 hexagon are 17.75 Å × 12.96 Å. In order to stabilize the
whole structure, two 2D porous networks interlace with
each other to produce a 2-fold interpenetrating layer (Fig.
bond angles around Zn1 range from 101.15(17)° to
122.56(8)°, and the bond angles around Zn2 vary from
97.64(18)° to 123.71(10)°. The average Zn–Cl bond
distance is 2.22 Å, and the average Zn–N bond distance is
3c). Furthermore, the adjacent layers are parallelly packed 75 2.06 Å.
and interact with each other through hydrogen bond
30 between coordinated water and lattice DMF molecules to
generate a supramolecular architecture. Wen et al. reported
Both 4-Hcptpy are neutral and act as bidentate ligands to
link two Zn(II) ions via outer pyridyl groups (mode V,
Scheme 2). The uncoordinated carboxyphenyl group is
twisted by 37.7° with respect to the central pyridyl ring to
a
complex {[Cd(4-cptpy)(Ac)(H2O)](DMA) (H2O)}n,
which is a 3D porous MOF and exhibits selective 80 relieve the steric effect. Careful observation finds that such
adsorption of CO2 and luminescence.8a
(a)
a connection between the 4-Hcptpy and Zn(II) ions results
in two kinds of 1D [Zn2(4-Hcptpy)2Cl4]n 21 helical chains
running along the b-axis, corresponding to left- and right-
handedness (both with a pitch of 14.06(9) Å, Fig. 4b).
85 Additionally, the carboxyl group of 4-Hcptpy remains
protonated and interacts via a hydrogen bond (O1–
H1A...O2#3 = 2.616(4) Å) with another carboxyl group in
adjacent parallel 1D chain to form a 2D supramolecular
network with hexagonal rings. Into the same layer, owing to
90 the alternate arrangement of the parallel left- and right-
handed helical chains, complex 5 undergoes racemization
and crystallizes in an achiral space group, Pnna.
Furthermore, along different directions, two kinds of weak
π−π interactions originate from the neighbouring phenyl
95 rings (centroid-to-centroid distance of 3.910 Å), and pyridyl
rings (centroid-to-centroid distance of 3.790 Å) of adjacent
helical chains, which further extend the whole structure to a
3D supramolecular framework. (Fig. S4, ESI). Recently, a
35
40
45 (b)
50
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Dalton Transactions
1D ribbon polymer [Zn(3-cptpy)Cl]n was reported, in which 40 distortion, coordinated by four oxygen atoms and two
3-cptpy− displays tetradentate coordination mode I (Scheme
2).8c
nitrogen atoms from four disparate 3-cptpy− ligands. As
listed in Table S1 (ESI), the bond distances and angles
around four cobalt ions are slightly different. All the Co–O
bond distances fall in the range of 2.021(9)-2.199(6) Å,
45 and Co–N bond distances vary from 2.162(2) to 2.250(2) Å.
Four 3-cptpy− ligands all serve as tetradentate ligands,
each coordinates to four Co(II) ions through bridging
carboxyl group and two outer pyridyl groups (mode VI,
Scheme 2). Every Co(II) ion is combined with one
50 monodentate formate with an average Co–O bond distance
of 2.091 Å. Interestingly, two types of Co2 dimers
[Co2(COO)2(H2O)] are formed with the connections of
coordinated water and bridging carboxyl groups, brief as
Co1&Co2’ and ‘Co3&Co4’. The Co···Co separations are
55 3.703(6) Å for the former, and 3.655(7) Å for the latter. As
connection nodes, these Co2 dimers are further linked by 3-
cptpy− to construct a 2D polymeric network with the
shortest distance of 10.502 Å between the Co2 dimers, as
shown in Fig. 5b.
5
10
15
20
25
(a)
(b)
60 (a)
65
30 Fig. 4 (a) The asymmetric unit of 5; (b) perspective view
of the 2D supramolecular network built by 1D left- and
right-handedness helical chains.
70
(e)
Structure of [Co4(3-cptpy)4(HCOO)4(H2O)2]n (6).
Complex 6 is a 3-cptpy-based complex, which possesses a
35 2D bilayer polymeric network. The asymmetric unit
contains four independent Co(II) ions, four 3-cptpy−
ligands, four formate ligands and two coordinated water
molecules (Fig. 5a). Four distinct Co(II) ions all exhibit
cis-octahedral geometries with different degrees of
75
80
85
6
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Dalton Transactions
Page 8 of 13
Fig. 5 (a) The asymmetric unit of 6; (b) perspective view of the 2D polymeric network; (c) the 2D bilayer network of 6.
The ‘Co1&Co2 dimer, ‘Co3&Co4’ dimer, upper layer 3-cptpy−, and lower layer 3-cptpy− are marked as orange, pink, red
and blue, respectively; (d) the 3.6 two-nodal topology; (e) view of the sandwich-like 3D supramolecular architecture
stacking via intermolecular π−π interactions.
5
Careful observation into this 2D framework indicates
that the 3-cptpy− ligands could be classified into two
categories, ‘upper layer linkers’ and ‘lower layer linkers’,
which produce a bilayer network where Co2 dimers are
embedded (Fig. 5c). Regarding two kinds of 3-cptpy–
55
10 ligands and Co2 dimers respectively as three-connected and
six-connected nodes, the whole framework of 6 can be
toplogically represented as a (3,6)-connected net with
Schlafli symbol {42.6}2{44.69.82} (Fig. 5d). Ultimately,
due to the weak intermolecular π−π stacking interactions
15 from aromatic rings that belong to adjacent layers, these
2D networks are packed into a sandwich-like 3D
supramolecule (Fig. 5e).
(b)
60
Structure of [Mn(3-cptpy)2]n (7). Complex 7 is a 2D 65 (c)
coordination polymer constructed by 3-cptpy− ligand. The
20 asymmetric unit consists of one Mn(II) ion and two 3-
cptpy− ligands. As shown in Fig. 6a, Mn1 is six-
coordinated with a slight distorted octahedral geometry.
Fig. 6 (a) The asymmetric unit of 7; (b) perspective views
of the 2D network and 1D linear Mn cluster; (c) the 3.6
The equatorial plane is completed by four O atoms from 70 two-nodal kgd topology. The 3-cptpy− ligands and Mn(II)
four bridging carboxyl groups, while the axial positions are
25 occupied by two pyridyl nitrogens with a N1–Mn1–N2
bond angle of 175.17(12)°. The Mn–O bond distances vary
from 2.167(3) to 2.196(3) Å, and the average Mn–N
distance is 2.313(4) Å.
Both 3-cptpy– ligands are tridentate and adopt the
30 coordination mode VII (Scheme 2). In terms of the steric
environment, benzene rings of two distinct 3-cptpy−
ligands rotate by nearly the same angles with respect to
ions are marked as green and purple, respectively.
Comparison of Hcptpy coordination modes. As
summarized in Scheme 2, seven distinct coordination
modes of 4/3-Hcptpy, presenting in complex 1−7, are well
75 depicted. Unlike the 2-Hcptpy, due to the steric hindrance
effect, the weak coordination ability of the central pyridyl
group in 4/3-Hcptpy can be confirmed. Indeed, the central
pyridyl groups in all reported 4/3-Hcptpy complexes are
uncoordinated.8 It is also discovered that the rigid 4/3-
their central pyridyl groups, presenting 31.0° and 29.5°, 80 Hcptpy ligands normally can be simplified into three-
respectively. As shown in Fig. 6b, a 2D network is
35 constructed based on the well-organized connection
between Mn(II) nodes and 3-cptpy− linkers. The 1D linear
Mn polynuclear clusters are included into this 2D network
connected and two-connected nodes as building blocks,
acting as three-connected junctions for complexes 4, 6 and
7, and as two-connected knots in complexes 1, 2, 3 and 5.
We believe that this directed expansion capability will
by Mn-(COO)2-Mn linkages. Acting as unique second 85 make 4/3-Hcptpy as good candidates for rational design
building blocks, these metallic clusters combine with
40 pyridyl groups to extend the whole architecture along bc
plane. To simplify the entire framework into node and
connection net, taking 3-cptpy− ligands and Mn(II) ions for
three-connected and six-connected nodes respectively,
complex 7 exhibits a (3.6) two-nodal kgd topology with
45 the Schlafli symbol {43}2{46.66.83} (Fig. 6c).
and assembly of target complexes in the future work.
Scheme 2. The coordination modes of 4/3-Hcptpy in
complexes 1–7
90
(a)
95
50
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Dalton Transactions
Syntheses and structural diversity. Complexes 1−7
supramolecular architectures of complexes 5 and 6.
were successfully prepared by hydro(solvo)thermal
reactions. As mentioned above, self-assembly process can
On the basis of the above observations, it can be found
that the pH value, solvent, and the coordination character
be heavily influenced by subtle changes of many factors. 55 of 4/3-Hcptpy all have significant effects on the structures
5
Through analysis and comparison, concerning the 4/3-
Hcptpy system and their derived coordination polymers,
some basic synthetic rules and structural features of the
frameworks can be summed up as follows:
of the resulting coordination polymers. In addition to this,
the synthetic strategy of complex 3 is being further
optimized for looking forward to a better yield and further
investigate its properties such as magnetic coupling.
a) Due to the existence of the carboxyl group, the type
60
Infrared spectra. The existences of 4/3-Hcptpy ligands
in seven complexes were confirmed by IR spectroscopy
(Fig. S5, ESI). The bands locate near 3070, 1600, and
1560 cm−1 are assigned, respectively, to the stretching
vibrations of C–H, C=C and C=N bonds of 4/3-cptpy.
10 and quantity of the alkaline reagent added in the reaction,
in other words, the pH value of the entire system has an
important impact on the final products. For example, a
mixture of 4-Hcptpy and NaOH in 1:1 molar ratio reacts
with Mn(II) salt produces a 3D metal–organic framework 65 While bands near 825 and 780 cm−1 can be designated to
15 (complex 1). However, reducing the pH value through
changing the ratio of 4-Hcptpy/NaOH to 2:1 will give rise
to an obviously different 2D Mn3 polymeric network with
flower-like pattern (complex 3). Moreover, the
δ(C–H) bending vibrations of pyridyl and phenyl groups.
The strong ν(COOH) absorption peak of 5 at 1685 cm−1
indicates that the carboxyl group of 4-Hcptpy remains
protonated. The carboxyl groups of 4/3-Hcptpy ligands in
deprotonated process of carboxyl acid can be conveniently 70 other six complexes are deprotonated.
20 completed by solvothermal reaction in DMF solution
without any addition of base. For complex 4, a 2D
hexagonal honeycomb microporous framework was built
in DMF solvent without alkaline reagent. We speculate that
Specifically, characteristic absorption bands at about
1600−1580 cm−1 correspond to the asymmetric stretching
vibrations of COO− group, whereas those at about
1420−1400 cm−1 are attributable to their symmetric
the decomposition of DMF at solvothermal conditions 75 vibrations. The separations between the νas(COO) and
25 could produce basic compound Me2NH, which promotes
the deprotonation procedure of the carboxyl group in
Hcptpy. Meanwhile, formate ligands were also observed in
complexes 4 and 6. Recently, Liu et al. prepared a complex
νs(COO) bands in 1, 2 and 4 are all less than 200 cm−1,
which confirm the bidentate chelating mode of the
carboxylate groups.17 In the IR spectrum of 4, the strong
absorption peak at 1662 cm−1 is ascribed to the stretching
(Me2NH)3[Mn6(HEBDC)4(H2O)8]·2DMF·H2O in DMF 80 vibration of carbonyl group (C=O) in lattice DMF
30 solution at 105 °C. Obviously, Me2NH is formed by the
decomposition of DMF.14 Similar DMF decomposition
behavior was also observed in complex (Me2NH)2[Cu9
(bshz)3(Py)10(C2H7N)(DMF)]·2DMF.15 This is why some
molecule. In addition, the bands near 3450 cm−1 are
associated with the coordinated and lattice water
molecules. These IR spectra are in good agreement with
the results of elemental analyses and X-ray structural
carboxylate complexes were prepared in DMF solution 85 characterizations.
35 without alkaline additive in recent research.16 In contrast
with 4, the solvothermal reaction of complex 5 in ethanol
without alkaline additive afforded a 1D 21 helical chain
structure, in which the carboxyl group remains protonated,
Thermogravimetric analyses. In order to investigate
the thermal stabilities of 4-Hcptpy complexes, the thermal
behaviors of complexes 1 and 2 are chosen to be tested by
TG-DSC (Fig. S6, ESI). The experiments are performed
thus restricting the extension of the architecture. It is well- 90 on solid samples consisting of numerous single crystals in
40 known that metal-hydroxide precipitates are easily
produced when preparing carboxylate complexes using
NaOH and triethylamine as bases. Now we can prepare
carboxylate complexes conveniently under solvothermal
conditions in DMF solution without any basal additive.
the 20−800 °C temperature range under N2 atmosphere.
Based on the isostructural frameworks of 1 and 2, both
complexes exhibit similar TG curves and maintain
structural stabilities under 440 ºC. In the 440−500 ºC range,
95 both complexes exhibit an explosive decomposition,
corresponding to the loss of partial 4-cptpy− ligands. The
intermediates could be [Mn(ph-COO)2] for 1 (found,
65.96%; calcd, 61.05%), and [Co(ph-COO)2] for 2 (found,
66.13%; calcd, 60.56%). After that, the intermediates
45
b) Based on the intrinsic triangular rigid skeletons of
4/3-Hcptpy ligands, porous metal–organic frameworks are
easy to be constructed. Hexagonal pores with various
dimensions are found in complexes 1, 2, 4 and 5.
Additionally, the intermolecular π−π stacking interactions 100 begin to decompose gradually in 520−620 ºC, losing the
50 stemming from the large π-conjugated structures of the
remaining 4-cptpy− ligands. The final residues are MnO2
4/3-Hcptpy ligands contribute a lot to the stability of the
for 1 (found, 8.74%; calcd, 11.32%) and CoO for 2 (found,
8
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DOI: 10.1039/C3DT52500G
8.07%; calcd, 9.81%).
value of complex 1 decreases continuously from 8.35 to
1.00 cm3·K·mol−1. Considering that the Mn2 cluster is
isolated by larger 4-cptpy ligands, the appropriate magnetic
exchange pathway in (µ-O2CR)2Mn2 core is through the
55 bidentate carboxylate bridges. Due to the magnetic couple
is located at Mn2 unit (S1 = S2 = 5/2), a theoretical
susceptibility equation based on the spin Hamiltonian (H =
−2J S1·S2) is employed to evaluate the magnetic exchange
constant by fitting the magnetic susceptibility data.20 This
60 gives the singlet-triplet energy separation value J = −0.49
cm−1, g = 1.97, and an agreement factor R of 1.62 × 10−2.
This result indicates the presence of weak
antiferromagnetic interaction in the Mn2 dimer. In the
period of 38−50 K, the χMT value slightly increased by
65 lowering the temperature, indicating a weak ferromagnetic
coupling existing between adjacent Mn2 dimers.
Complex 2 is isostructural with complex 1, and has
similar χMT−T curve. A theoretical susceptibility equation
suitable for Co2 unit (S1 = S2 = 3/2) is employed to
70 evaluated the magnetic exchange constant by fitting the
magnetic susceptibility data in 35−300 K.21 This gives the
singlet-triplet energy separation value J = −2.56 cm−1, g =
2.49, and an agreement factor R of 3.12 × 10−4. This result
indicates a weak antiferromagnetic interaction existing in
75 the Co2 dimer.
Photoluminescence. Considering the large π-conjugated
structure of rigid 4-Hcptpy ligand and the varied
luminescent behaviors of d10 transition metal complexes,18
we investigate the luminescent behavior of Zn(II) complex
5 in the solid state at room temperature (Fig. 7). When
excited with 329 nm light, the Zn(II) complex 5 acts as a
strong violet luminescent emitter with an emission
maximum at 383 nm. To understand the emission
10 mechanism, the luminescence of 4-Hcptpy ligand is
determined for comparison. With similar excitation at 329
nm, 4-Hcptpy exhibits an emission peak centered at 381
nm, assigned to the intraligand π*→π transition. Therefore,
similar emission energy between the tested complex and
15 the 4-Hcptpy ligand indicates that the luminescent
mechanism of 5 originates from ligand-centered emission.
The enhancement of the intensity of 5 could be attributed
to the unique coordination of 4-Hcptpy to the Zn(II) center,
which increases the conformational rigidity of the ligand.
20
5
25
30 Fig. 7 Emission spectra of Zn(II) complex 5 and 4-Hcptpy
ligand.
80
Magnetic properties. For the magnetic properties of
cptpy complexes, Zhao et al. reported two novel 2D 3d−4f
networks based on planar Co4Ln2 clusters supported by
35 rigid 2-Hcptpy ligand, which perform single-molecule
magnet behaviors.19 This finding promotes us to
investigate the magnetic properties of 4-Hcptpy complexes
1 and 2, which contain Mn2 and Co2 dimers.
85 Fig. 8 The plots of χMT vs. T for 1 (left) and 2 (right). The
solid red line represents the best theoretical fit.
Conclusions
The temperature dependence of magnetic susceptibilities
40 of [Mn(4-cptpy)2]n (1) and [Co(4-cptpy)2]n (2) were
measured in the temperature range of 2−300 K at a
magnetic field of 1000 Oe. The variation of χMT versus T
is plotted in Fig. 8. For complex 1, the χMT value per Mn2
unit at 300 K is 8.35 cm3·K·mol−1, which is close to the
45 spin-only value (8.37 cm3·K·mol−1 with g = 2.0) of two
Mn2+ ions (S = 5/2). For complex 2, the χMT value per Co2
unit at 300 K is 5.72 cm3·K·mol−1, which is also close to
the value expected for spin-only value of two Co2+ ions
(5.48 cm3·K·mol−1 with g = 2.0, S = 3/2).
Based on the rigid triangular-shaped 4/3-Hcptpy ligands,
90 seven coordination polymers with dimensional diversity
from 1D to 3D have been successfully prepared and
structurally characterized. Among 1−7, 4/3-Hcptpy ligands
act as three- or two-connected nodes and present up to
seven coordination modes. The detailed investigation
95 reveals that the overall structures of complexes could be
affected by multi-factors, such as pH value, solvent, and
weak intermolecular interactions. A generally solvothermal
method is proposed for preparing carboxylate complexes in
DMF solution without any basal additive. Antiferro-
100 magnetic interactions were detected in the discrete
50
Upon cooling of the sample from 300 to 2 K, the χMT
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Page 11 of 13
Dalton Transactions
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dinuclear Mn/Co clusters of complexes 1 and 2, which also
possess high thermal stabilities. Zn(II) complex 5 is
confirmed to be a strong violet luminescent emitter. 4/3-
Hcptpy ligands can be considered as two potential
multidentate rigid ligands for systematical design of
coordination polymers and MOFs. The further study for
the magnetic behavior of complex 3 is still under way.
55
60
65
70
75
80
85
5
Acknowledgments
This work was financially supported by National Natural
6
10 Science Foundation of China (21171115, 21203117) and
Innovation Program (12ZZ089) of Shanghai Municipal
Education Commission.
Notes
†Electronic Supplementary Information (ESI) available: Selected
15 bond distances and angles, IR spectra and TGA curves. CCDC
reference numbers 943673–943677, 943680 and 943681. For ESI
and crystallographic data in CIF or other electronic format see
DOI: 10.1039/b000000x/
7
8
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DOI: 10.1039/C3DT52500G
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Table 1. Crystallographic data and structure refinement for complexes 1−7
1
2
3
formula
fw
cryst syst
space group
a (Å)
C44H28N6O4Mn
759.66
monoclinic
P21/c
9.299(12)
21.109(3)
19.378(2)
90
C44H28N6O4Co
763.65
C132H90N18O15Mn3
2333.05
triclinic
monoclinic
P21/c
9.456(8)
20.560(18)
19.480(15)
90
Pī
10.644(1)
17.496(2)
30.022(3)
98.411(2)
91.251(2)
96.172(2)
5494.9(10)
2
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V [Å3]
104.356(5)
90
105.539(3)
90
3685.1(8)
4
3648.8(5)
4
Z
Dc (g cm−3)
µ (mm−1)
reflections/ unique
Rint
1.369
1.390
1.410
0.418
0.411
0.524
19096/6511
0.0821
22740/8367
0.0605
36209/21392
0.0557
data/restraints /params 6511/0/496
8367/0/496
1.236
21392/103/1491
1.030
GOF on F2
1.113
0.0625, 0.0888
0.0524, 0.0709
0.1036, 0.2783
R1, wR2 (I > 2σ(I))
largest diff. peak and
hole (e Å−3)
0.358, −0.388
0.291, −0.377
1.170, −1.051
4
5
6
7
C26H24N4O6Co
547.42
monoclinic
P21/n
C48H44Cl4N6O7Zn2
1089.43
orthorhombic
Pnna
C92H64N12O18Co4
1861.27
triclinic
Pī
C44H28N6O4Mn
759.66
triclinic
Pī
7.291(1)
26.677(5)
12.932(2)
90
106.170(2)
90
16.766(1)
14.069(1)
20.444(2)
90
90
90
11.702(1)
18.389(2)
20.506(3)
113.866(1)
101.406(2)
95.164(2)
9.962(4)
10.641(4)
17.524(7)
86.709(5)
79.071(5)
66.811(3)
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 11

View Article Online
DOI: 10.1039/C3DT52500G
Page 13 of 13
Dalton Transactions
2415.7(7)
4
4822.7(8)
4
3883.8(9)
2
1676.3(11)
2
1.505
0.761
1.500
1.274
1.592
0.925
1.505
0.452
14165/5452
0.0698
23767/4271
0.0362
24369/17112
0.0187
10495/7349
0.0244
5452/0/336
1.143
4271/1/287
1.041
17112/0/1135
1.021
7349/102/496
1.406
0.0938, 0.1647
0.465, −0.807
0.0478, 0.1287
0.677, −0.896
0.0410, 0.0998
0.561, −0.309
0.1111, 0.3386
3.387, −0.751
12 | Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]