Synthesis, crystal structure and optical property of three coordination polymer constructed from m-phenylenediacrylate acid

Article abstract of DOI:10.1016/j.jssc.2014.09.015

Three new complexes of the wholly deprotonated flexible ligand m-phenylenediacrylate acid (H₂mpda), namely, [Zn (mpda) (H₂O)] [1], [Pr₂(mpda)₂(H₂O)₂(CHOO)₂] [2], and [Mn₂

Full text of DOI:10.1016/j.jssc.2014.09.015

Journal of Solid State Chemistry 221 (2015) 37–48
Contents lists available at ScienceDirect
Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Synthesis, crystal structure and optical property of three coordination
polymer constructed from m-phenylenediacrylate acid
n
YiFan Xiao, TingTing Wang, HePing Zeng
School of Chemistry and Chemical Engineering, State Key Laboratory of Luminescent Materials, South China University of Technology, Guangzhou 510641,
Guangdong, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 17 July 2014
Received in revised form
6 September 2014
Accepted 14 September 2014
Available online 28 September 2014
Three new complexes of the wholly deprotonated flexible ligand m-phenylenediacrylate acid (H2mpda),
namely, [Zn (mpda) (H2O)] [1], [Pr2(mpda)2(H2O)2(CHOO)2] [2], and [Mn2(mpda)2 (H2O)4] [3], were
synthesized by the solvothermal reaction. The complexes were characterized by IR spectroscopy,
thermogravimetric analysis, and X-ray single-crystal diffraction. A mixed sample [Nd(mpda)(H2O)
(CHOO) ꢀ Pr(mpda)(H2O)(CHOO)] [2"] was also synthesized and studied. Compounds [1] and [2] exhibit
a selective sensing function with respect to acetone, and they are a potential luminescent sensory
material for the selective detection of Zn2þ and Ni2þ ions, respectively. Furthermore, the fluorescent
changes of compound [1] upon the addition of cations (Fe3þ and Zn2þ, Bi2þ and Zn2þ) are utilized to
construct two logic gates at the molecular level.
Keywords:
m-Phenylenediacrylic acid
Coordination polymers
Crystal structure
Fluorescence
& 2014 Elsevier Inc. All rights reserved.
1. Introduction
they reported three 2D Zn(II) metalꢁorganic frameworks exhibit-
ing different 2D-to-2D interpenetrating topologies. These were
Metal–organic frameworks (MOFs) have gained great attention
in recent years due to their interesting structure and topologies as
well as their potential applications as zeolite-like materials [1–7].
The designed synthesis of coordination networks is a difficult
challenge in most cases, due to the synthetic conditions required,
such as metal ions, organic dicarboxylic acid, coligand, solvent and
noncovalent interactions such as hydrogen bonding and π–π
stacking [8,9]. The porosity within some MOF-based transition
and lanthanide metals makes them excellent candidates for
luminescent sensors. So far, research on molecular sensing by
non-porous MOFs is very scarce [10,11]. Following iron, zinc ranks
the second most abundant transition metal in the human body,
playing a vital role in many biological processes, such as cellular
metabolism, gene expression, and immune function [12]. Nickel
can cause nasal and lung cancer, dermatitis, asthma, and disorders
of the central nervous system [13]. Therefore it is necessary to
develop Zn2þ and Ni2þ sensors that possess selective and sensi-
tive signaling mechanisms.
synthesized via solvothermal reactions of m-phenylenediacrylic
acid(H2mpda) and zinc(II) salts in the presence of different bis
(pyridyl)ancillary ligands [15]. Later they synthesized a lanthanide(III)
coordination polymer with mixed m-phenylenediacrylate (mpda)
and formate bridges, [Nd (mpda) (HCOO) (H2O)]n. Liu [16] synthe-
sized a Zn coordination polymer compound using mpda as auxiliary
ligand.
In this work, we chose m-phenylenediacrylate acid (H2mpda)
for building coordinate networks with diverse topologies.
Although the ditopic symmetry of H2mpda and its derivatives or
its analogs have wide applications in the field of solid-state
photosensitive materials [17,18], H2mpda has not been well
exploited in building MOFs. To our knowledge, few metal com-
plexes of H2mpda have been reported.
Here, we report the synthesis and structures of three metal–
organic coordination polymers of mpda with metal ions (Zn,
Pr, Mn) formulated as [Zn (mpda)(H2O)] [1], [Pr2(mpda)2(H2O)2
(CHOO)2] [2], and [Mn2(mpda)2 (H2O)4] [3]. These three metalꢁ
organic frameworks exhibit 2D, 3D, and 1D structures, respectively.
Furthermore, characterization of complexes [1], [2], and [3] was
investigated. In addition, because compound [2] and reported
sample [Nd2(mpda)2(H2O)2(CHOO)2][20] [19] are isomorphous
MOFs, and their synthetic methods are basically the same, the
mixed sample [Nd(mpda)(H2O)(CHOO)ꢀ Pr(mpda)(H2O)(CHOO)]
[200] has been synthesized and studied. Finally, we studied the
fluorescence sensing performance of these compounds to solvent
Sun et al. [14] reported four novel metal–organic coordination
polymers with two different phenylenediacrylate ligands: p-phe-
nylenediacrylate and m-phenylenediacrylate. This was the first
report of a MOF-based m-phenylenediacrylate ligand. Subsequently
n
Corresponding author.
E-mail address: hpzeng@scut.edu.cn (H. Zeng).
http://dx.doi.org/10.1016/j.jssc.2014.09.015
0022-4596/& 2014 Elsevier Inc. All rights reserved.

38
Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
and metal ions. Compounds [1] and [2] exhibit a selective sensing
function with respect to acetone, Zn2þ and Ni2þ. It was also found
that compound [1] could act as two fluorescent logic gates operated
by two chemical inputs (Fe3þ and Zn2þ, Bi2þ and Zn2þ).
2.2.3. Synthesis of Pr2(mpda)2(H2O)2(CHOO)2 [2]
A
mixture of PrCl3 ꢀ 6H2O (0.1 mmol, 0.03 g), H2mpda
(0.1 mmol, 0.022 g), in dimethyl formamide (DMF) (2 mL) and
H2O (2 mL) was heated in a 23 mL Teflon-lined autoclave at 120 1C
for 1 day. After being cooled to room temperature, green blocks of
crystals of [2] were isolated in yield 58%.
2. Experimental section
C
26H22O14Pr2: calcd. C 48.43%; H 3.42%; found: C 48.16%; H
3.31%. IR (KBr, cmꢁ1):¼3420, 2890, 2024, 1644, 1440, 1346, 1381,
2.1. Materials and methods
1272, 1103, 868, 780, 678.
All of the solvents and reagents for synthesis were commercially
available. Elemental analysis was carried out with a Carlo Erba 1106
fully-automatic trace organic elemental analyzer. FT-IR spectra were
recorded from KBr pellets in the range of 4000–400 cmꢁ1 on a Bruker
EQUINOX-55 spectrometer. Fluorescence spectra were performed on a
Hitachi F-4500 fluorescence spectrophotometer at room temperature.
Thermogravimetric analyses (TGA) were performed under nitrogen
with a heating rate of 10 1C/min using a Q600 SDT thermogravimetric
analyzer. Variable-temperature powder X-ray diffraction (PXRD) was
carried out on a Shimadzu XRD-7000 analyzer.
2.2.4. Synthesis of Mn2(mpda)2 (H2O)4 [3]
A
mixture of MnCl3 ꢀ 6H2O (0.1 mmol, 0.03 g), H2mpda
(0.1 mmol, 0.022 g), in DMF (2 mL) and H2O (2 mL) was heated
in a 23 mL Teflon-lined autoclave at 90 1C for 1 day. After being
cooled to room temperature, brown blocks of crystals of [3] were
isolated in yield 35%.
C
24H24Mn2O12: calcd. C 46.90%; H 3.91%; found: C 46.57%;
H 3.29%. IR (KBr, cmꢁ1):¼3837, 2376, 1634, 1440, 1523, 1443,
1349, 985, 873, 802, 619.
2.2. Synthesis
Table 2
2.2.1. Synthesis of H2mpda
Selected interatomic distances (Å) and angles (deg) for compounds 1–3.
m-Phenylenediacrylate acid (H2mpda) was prepared according
to the literature [20]. A suspension of 1, 3-benzenedicarboxaldehyde
(500 mg, 3.7 mmol), malonic acid (1.72 g, 16.5 mmol), and pyridine–
piperidine (70:1 v/v, 7 mL) was heated at reflux for 24 h. After
cooling, the mixture was adjusted to pH 1 by the addition of 1 N HCl
solution. The resulting precipitates were collected by filtration,
washed with water, and then dried in vacuo to give a white powder.
1
Zn1–O4i
1.938(6)
1.956(6)
1.956(6)
117.0(3)
110.9(2)
99.5(3)
107.4(3)
100.0(3)
99.5(3)
Zn1–O1
1.950(6)
1.980(7)
1.938(6)
110.9(2)
118.9(3)
118.9(3)
107.4(3)
100.0(3)
Zn1–O2ii
Zn1–O5
O2–Zn1iii
O4–Zn1iv
O4i–Zn1–O1
O4i–Zn1–O2ii
O2ii–Zn1–O5
O4i–Zn1–O5
O1–Zn1–O5
O2ii–Zn1–O5
O4i–Zn1–O2ii
O1–Zn1–O2ii
O1–Zn1–O2ii
O4i–Zn1–O5
O1–Zn1–O5
2.2.2. Synthesis of Zn (mpda)(H2O)[1]
A
mixture of Zn(NO3)2 ꢀ 6H2O (0.1 mmol, 0.03 g), H2mpda
(i)x, y, 1þz; (ii) 1ꢁx, 0.5þy, 1ꢁz; (iii) 1ꢁx, ꢁ0.5þy, 1ꢁz; (iv) x, y, ꢁ1þz.
(0.1 mmol, 0.022 g), in N, N-dimethyl acetamide (DMA) (2 mL)
and H2O (4 mL) was heated in a 23 mL Teflon-lined autoclave at
120 1C for 1 day. After being cooled to room temperature, yellow
blocks of crystals of [1] were isolated in yield 64%.
2
Pr1–O6i
2.416(11)
2.507(11)
2.541(11)
2.583(12)
141.6(4)
140.7(4)
66.8(4)
130.0(4)
70.1(4)
78.4(4)
Pr1–O3ii
Pr1–O5
Pr1–O4
Pr1–O7
2.482(12)
2.525(11)
2.545(12)
2.621(13)
122.0(3)
36.7(2)
Pr1–O2ii
Pr1–O1
Pr1–O5ii
C
12H10O5Zn: calcd. C 48.33%; H 3.39%; found: C 47.81%; H 3.93%
IR (KBr, cmꢁ1):¼3414, 2024, 1641, 1618, 1509, 1449, 1381, 1272,
O6i–Pr1–O3ii
O6i–Pr1–O2ii
O3ii–Pr1–O2ii
O6i–Pr1–O5
O3ii–Pr1–O5
O2ii–Pr1–O5
O6i–Pr1–O1
O4–Pr1–Pr1ii
O5ii–Pr1–Pr1ii
O7–Pr1–Pr1ii
O2–Pr1–Pr1ii
O3–Pr1–Pr1ii
Pr1iii–Pr1–Pr1ii
1163, 969, 900, 772, 618.
84.5(3)
124.1(3)
157.5(2)
129.66(5)
Table 1
Crystal data and structure refinement results for 1, 2 and 3.
69.2(4)
1
2
3
(i) x, 1.5ꢁy, 0.5þz; (ii) 1ꢁx, 0.5þy, 1.5ꢁz; (iii) 1ꢁx, ꢁ0.5þy, 1.5ꢁz.
Empirical formula
Formula weight
C12H10O5Zn
299.57
C26H22O14Pr2
840.26
C24H24Mn2O12
614.31
3
Mn1–O1
2.122(4)
2.157(3)
2.249(4)
2.067(4)
2.150(3)
Mn1–O7
Mn1–O9
Mn1–O3
Mn2–O8
Mn2–O12
Mn2–O1
2.123(4)
2.177(3)
2.287(4)
2.076(4)
2.182(4)
2.341(4)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Monoclinic
P2(1)
7.5773(11)
6.5414(7)
11.8375(16)
90.00
Monoclinic
P2(1)/c
13.6052(11)
7.3672(5)
13.2676(12)
90.00
Monoclinic
P2(1)/c
26.635(3)
7.6484(6)
12.8629(11)
90.00
Mn1–O10
Mn1–O4
Mn2–O5
Mn2–O11
Mn2–O2
Mn1–O1
2.305(3)
α (1)
2.122(4)
β (1)
102.040(2)
90.00
573.83(13)
2
1.73367
304
2.94–24.99
1969
1574
0.0676
1.041
0.0605
0.1302
98.8680(10)
90.00
1313.94(18)
2
2.12368
816
3.11–25.02
2284
1805
0.0000
1.071
0.0785
103.911(2)
90.00
2543.5(4)
4
1.604
1256
2.778–25.092
4468
3519
0.0000
1.039
0.0482
O1–Mn1–O7
O1–Mn1–O10
O7–Mn1–O10
O1–Mn1–O9
O7–Mn1–O9
O10–Mn1–O9
O1–Mn1–O4
O7–Mn1–O4
O10–Mn1–O4
O9–Mn1–O4
O1–Mn1–O3
O7–Mn1–O3
O10–Mn1–O3
O9–Mn1–O3
O4–Mn1–O3
98.24(15)
87.96(13)
93.32(13)
87.91(14)
96.07(12)
170.19(13)
171.44(13)
89.00(15)
96.22(13)
86.78(13)
115.21(14)
146.54(15)
88.06(12)
85.66(12)
57.67(13)
O5–Mn2–O8
O5–Mn2–O11
O8–Mn2–O11
O5–Mn2–O12
O8–Mn2–O12
O11–Mn2–O12
O5–Mn2–O2
O8–Mn2–O2
O11–Mn2–O2
O12–Mn2–O2
O5–Mn2–O1
O8–Mn2–O1
O11–Mn2–O1
O12–Mn2–O1
O2–Mn2–O1
111.20(15)
94.20(14)
87.89(14)
86.59(15)
90.01(15)
177.90(15)
99.64(14)
149.15(15)
91.09(12)
90.70(12)
154.78(14)
93.82(14)
89.67(13)
90.44(14)
55.33(12)
γ (1)
V (Å3)
Z
Dcalcd (g cmꢁ3
F (0 0 0)
)
Theta range
Reflections collected
Reflections unique
R(int)
Goodness-of-fit on F2
R1 [I42σ(I)]
wR2[I42σ(I)]
R1 (all data)
wR2 (all data)
0.1950
0.0961
0.2123
0.1082
0.0664
0.1187
0.0790
0.1502

Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
39
2.2.5. Synthesis of Nd2(mpda)2(H2O)2(CHOO)2 [20]
[Nd(mpda)(H2O)(CHOO)] [20] was synthesized according to the
method reported previously [19].
data are summarized in Table 1. Selected bond lengths and angles
for [1], [2], and [3] are listed in Table 2.
2.4. Fluorescence measurements
2.2.6. Synthesis of [Nd(mpda)(H2O)(CHOO) ꢀ Pr(mpda)(H2O)(CHOO)]
[200]
The PL properties of [1], [2], and [3] and free ligand mpda were
investigated in solid-state and in various solvent emulsions at
room temperature. The [1] and [2] solvent emulsions were
prepared by introducing 5 mg of [1] or [2] powder into 5.00 mL
of methanol, ethanol, DMF, dichloromethane, DMA, acetone, tert-
Butanol, acetonitrile or THF. The metal ion interaction studies were
A mixture of PrCl3 ꢀ 6H2O (0.1 mmol, 0.03 g), Nd(NO3)3_6H2O
(0.1 mmol, 0.044 g), H2mpda (0.2 mmol, 0.044 g), in DMF (2 mL)
and H2O (2 mL) was heated in a 23 mL Teflon-lined autoclave at
120 1C for 1 day. After being cooled to room temperature, gray
blocks of crystals of [2"] were isolated in yield 72%.
performed by addition of nitrate salts of Zn2þ, Cd2þ, Pb2þ, Fe3þ, Bi3þ
,
Ni2þ, Al3þ, Co2þ, Agþ, and Ce3þ to DMF emulsions of [1] or [2], with
the concentration of the metal ion of 1.0 ꢂ 10ꢁ4 M.
2.3. X-ray crystallography
Crystals of [1], [2], and [3] were selected for lattice parameter
determination and collection of intensity data at 296 K on a Bruker
Smart APEX II CCD diffractometer with monochromated Mo Kα
radiation (λ¼0.71073 Å) using a φꢁω scan mode. The structures
were solved by direct methods and refined on F2 by full matrix
least-squares using SHELXTL. All non-hydrogen atoms were
refined anisotropically. OꢁH hydrogens were located from different
electron density maps, and CꢁH hydrogens were placed in calcu-
lated positions and refined with a riding model. Crystallographic
3. Results and discussion
3.1. Crystal structure
3.1.1. Crystal structure of Zn (mpda)(H2O) [1]
X-ray analysis reveals that [1] crystallizes in monoclinic space
group P2(1). As shown in Fig. 1a, [1] consists of one crystal-
lographically independent Zn(II) ion, one mpda ligand, and one
Fig. 1. (a) Coordination environment of Zn in compound [1]. (b) SBU[ZnO3] is connected by mpda to form a network in [1]. (c) The double deck structure and 3D network
formed by the H-bond of [1]. (d) Schematic diagram (OLEX) showing the 4-connected (6,3) network of compound [1].

40
Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
M
M
M
O
C
M
O
C
O
O
M
M
O
C
C
O
O
O
1
2
M
M
M
O
O
O
O
C
O
C
M
M
M
C
C
O
O
O
Scheme 1. Crystallographically established coordination modes of carboxylic groups in compounds [1], [2], and two coordination modes [3].
Table 3
Fig. 2b reveals that the formate ions act as bridges and link Pr
Hydrogen bond lengths and bond angles for 1(Å).
(III) ions into a 2D layer, the mpda ligand serves as a V-shaped
pillar interlinking the Pr-formate layers to form a 3D network
(Fig. 2c). Mpda ligands act as 4-connected nodes to connect four Pr
and CHOOꢁ act as 3-connected nodes connecting three Pr atoms.
The ten-coordinated Pr can be considered as a 7-connected node.
The topology of this 3D network can be described as a {4.62}2{42.6}
{47.64.810} (Fig. 2d). In addition, there are nonstructural H-bonds
in [2]. Hydrogen-bonding details for [2] are given in Table 4.
Donor⋯H⋯Acceptor D–H
H⋯A
(Å)
D⋯A
(Å)
D–H⋯A
(1)
Symmetry
operation
(Å)
O(5)⋯H(5C)⋯O(3)
O(8)⋯H(5D)⋯O(3)
0.85
0.85
1.87
1.88
2.7065 167
2.7148 167
x, 1þy, 1þz
2ꢁx, 1/2þy, ꢁz
D¼Donor, A¼Acceptor.
coordinated water molecule. Each Zn(II) coordinates to three oxy-
gens of three mpda ligands and one oxygen of a water molecule.
The Zn has tetrahedral coordination, with bond lengths (Zn–O:
1.950(6), 1.956(6), 1.938(5) Å) for the mpda oxygens and (Zn–O:
1.980(7) Å) for the water oxygen. The mpda anions all adopt a
monodentate coordination mode (Scheme 1a).
Fig. 1b reveals the double deck structure of [1] similar to the
reported complex [21]. Two neighboring ZnO3 tetrahedra form a
binuclear cluster via carboxyl monodentate mode. The ZnO3
polyhedron is connected by mpda ligand to form 2D infinite
network (Fig. 1b). The 2D layers are further linked together via
intermolecular hydrogen bonds (O(5)–H(5D)⋯O(3) (2.71(10) Å,
166.5(50)1) to generate a 3D structure from the water molecule
(Fig. 1c). Hydrogen-bonding details for [1] are given in Table 3. The
total topology of [1] can be considered to be a (6, 3)-connected net
(Fig. 1d).
3.1.3. Crystal structure of Mn2(mpda)2 (H2O)4 [3]
X-ray analysis reveals that [3] crystallizes in monoclinic space
group P2(1)/c. As shown in Fig. 3a, compound [3] consists of two
crystallographically Mn(II) ions, two mpda ligand, and four coordi-
nated waters. Each Mn(II) coordinates to four oxygens of three
mpda ligands and two oxygens of two water molecules. The Mn1 is
octahedrally coordinated, bound to two oxygen atoms from two
water molecules (Mn1ꢁO: 2.157(3), 2.177(3) Å) in the apical posi-
tions and four oxygen atoms from three mpda ligands (Mn1ꢁO:
2.122(3)–2.287(4) Å) in the equatorial positions. The Mn2 is also
octahedrally coordinated, bound to two oxygen atoms from two
water atoms (Mn2ꢁO: 2.182 (3), 2.150(3) ) and four oxygen atoms
from three mpda ligands (Mn2ꢁO: 2.068(3)–2.341(3) Å).
The mpda anions adopt two coordination modes: (1) one
carboxyl group adopts a chelating coordination mode to bridge
two Mn centers, and the other carboxylate group chelates a single
Mn (Scheme 13a). (2) One carboxylate group coordinates to two Mn
centers by adopting a monodentate coordination mode, and the
other carboxylate group coordinates to one Mn by adopting a
monodentate coordination mode (Scheme 13b). Two Mn (II) atoms
are bridged by two carboxylates to form a binuclear cluster with
Mn(1)⋯Mn(2) separation of 3.879(1) Å. As shown in Fig. 3b, two
neighboring binuclear clusters of Mn(II) are bridged by two mpda to
form a closed loop. The framework is a 1D infinite catenarian
network. The 1D chains construct a 2D plane structure through π–π
stacking (Fig. 3c). Furthermore, this plane structure is linked by
hydrogen-bonding to form a 3D structure (Fig. 3d). Hydrogen-
bonding details for [3] are given in Table 5.
3.1.2. Crystal structure of Pr2 (mpda)2(H2O)2(CHOO)2 [2]
Compound [2] is an isomorphic compound of the previously
reported MOF [Nd(mpda)(HCOO)(H2O)]n [19]. They have the same
topology but different lanthanide (III) ions. X-ray analysis reveals
that [2] crystallizes in monoclinic space group P2(1)/c. As shown in
Fig. 2a, the asymmetric unit consists of two crystallographically
Pr (III) ions, two mpda ligands, and two coordinated waters. Each Pr
(III) coordinates to six oxygens of four mpda ligands (PrꢁO: 2.482
(12)–2.869 (13) Å), three oxygens of three formate (PrꢁO: 2.541(11),
2.416(11) Å), and one oxygen from water (PrꢁO: 2.621(13) Å). The
mpda anions all adopt a bidentate coordination mode to bridge two
Pr centers (Scheme 1b).

Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
41
Fig. 2. (a) Coordination environment of Pr in compound [2]. (b) Pr center connected by CHOOꢁ to form 2D infinite plane in [2]. (c) SBU connected by mpda to form 3D
infinite network in [2]. (d) Topological representation of the network of [2]. Color code: green, Pr; red, formate; and blue, mpda. (For interpretation of the references to color
in this figure legend, the reader is referred to the web version of this article.)
can see that two isomorphous MOFs [2] and [20] and mixed
Table 4
compound [200] have similar patterns.
Hydrogen bond lengths and bond angles for 2(Å).
Donor⋯H⋯Acceptor D–H H⋯A
D⋯A
(Å)
D–H⋯A Symmetry operation
(1)
3.3. Fluorescence and UV–vis
(Å)
(Å)
O(7)⋯H(7A)⋯O(1)
O(9)⋯H(9)⋯O(6)
O(11)⋯H(11)⋯O(7) 0.93
O(12)⋯H(12)⋯O(4) 0.93
0.85
0.93
1.94
2.48
2.51
2.45
2.7768 168
3.2086 136
3.3909 158
2.7948 102
1ꢁx, 1ꢁy, 1ꢁz
x, 1þy, z
Fig. 4a shows the fluorescence emission spectra of compounds
[1] and [3] as well as the free ligand mpda upon excitation at
300 nm. The intense fluorescent emissions at 390 nm occur for all
three compounds, ascribed to the intraligand πn-π charge trans-
fer. Compounds [2], [20]and [2"] emit at 400 nm upon excitation at
254 nm (Fig. 4b), consistent with a band ascribed to intraligand
πn-π charge transfer.
1ꢁx, 1/2þy, 1/2ꢁz
ꢁx, 1þy, 1/2ꢁz
D¼Donor, A¼Acceptor.
3.2. XRD
Spectra in the UV–vis are shown in Fig. 5. Compared to the free
ligand mpda, the absorption peaks of compounds [1], [2], and [3]
have slightly red-shifted. The bands around 350 nm could be
assigned to characteristic π–πn transitions centered on the benzene
ring. The four absorption bands of [2] from 450 to 600 nm could
be assigned to 3H4-3P2, 3H4-3P1, 3H4-3P0 and 3H4-1D2 [22].
The experimental powder XRD pattern of compounds [1], [2],
and [3] are in good agreement with the corresponding simulated
ones except for the relative intensity variation, resulting from the
preferred orientation of the crystals (Fig. S2a–c). From Fig. S2d we

42
Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
Fig. 3. (a) Coordination environment of Mn in compound [3]. (b) 1D chain structure of [3]. (c) π–π stacking forms 2D network in compound [3]. (Centroid-to-centroid
distance is 3.781 Å.) (d) 3D network formed by H bond in compound [3].
observed at 1641, 1644 and 1634 cmꢁ1 in the spectra of [1], [2],
Table 5
Hydrogen bond lengths and bond angles for 3(Å).
and [3] (Fig. S3b–d). This significant shift was a result of coordina-
tion that took place through the carboxyl oxygen to the metal
atom.
Donor⋯H⋯Acceptor D–H
H⋯A D⋯A
D–
Symmetry operation
(Å)
(Å)
(Å)
H⋯A(1)
O(9)⋯H(9C)⋯O(2)
O(9)⋯H(9D)⋯O(6)
0.85
0.85
2.02
1.86
1.94
1.98
1.89
1.90
2.02
2.24
2.8442 162
2.6773 162
2.7596 162
2.7975 162
2.7309 170
2.7422 171
2.7765 149
3.0121 150
x, 1/2ꢁy, 1/2þz
ꢁx, 1/2þy, 1/2ꢁz
x, ꢁ1/2ꢁy, 1/2þz
ꢁx, ꢁ1/2þy, 1/2ꢁz
1ꢁx, 1/2ꢁy, 1/2ꢁz
ꢁx, 1/2þy, 1/2ꢁz
1ꢁx, ꢁ1/2þy, 1/2ꢁz
x, ꢁ1/2ꢁy, ꢁ1/2þz
3.5. Thermogravimetric analysis
O(10)⋯H(10C)⋯O(2) 0.85
O(10)⋯H(10D)⋯O(6) 0.85
C(11)⋯H(11C)⋯O(4) 0.85
C(11)⋯H(11D)⋯O(6) 0.85
C(12)⋯H(12C)⋯O(4) 0.85
C(12)⋯H(12D)⋯O(7) 0.85
To examine the thermal stabilities of these compounds, TG
analyses were carried out (Fig. 6). For compound [1], a rapid
weight loss is observed from 40 to 105 1C which is ascribed to
the loss of lattice water. Weight loss of 6% from 100 to 200 1C
corresponds to the loss of coordinated water molecule (calcd. 6%).
Then the organic ligands begin to decompose at 400 1C.
D¼Donor, A¼Acceptor.
The TG data for compound [2] show weight losses from 20 1C
to temperatures of 100ꢁ200 1C, assigned to the removal of
coordinated water molecules (calcd. 4.3%). At 420 1C, compound
[2] exhibits a series of weight losses attributed to the elimination
of organic cations, and the decomposition of the compound is
completed at 750 1C.
Since [2"] is a doping sample with metal ratio of 1:1, the
absorption peaks are made up of peaks from two pure samples
(Fig. 5b).
3.4. IR
Compound [3] shows a weight loss of 10% starting at 100 1C
and finishing at 180 1C, indicating the removal of solvents. The
next step starts at 280 1C and finishes at 350 1C. This loss
corresponds to loss of coordinated water molecules (calcd. 11.6%).
The FT-IR spectra of compounds [1], [2], and [3] are given in
Fig. S3. A strong band appears at 1740 cmꢁ1 in the IR spectrum of
free mpda and it was assigned to ν(C¼O) (Fig. S3a). This band was

Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
43
7000
6000
5000
4000
3000
2000
1000
0
2
2'
2''
2000
1800
1
1600
mpda
3
1400
1200
1000
800
600
400
200
0
-200
350
400
450
500
550
600
300
400
500
600
700
800
wavelength(nm)
wavelength(nm)
Fig. 4. (a) Fluorescent spectrogram of compounds [1] and [3], and the ligand in the solid state, all with excitation at 300 nm. (b) Fluorescent spectrogram of compounds [2],
[20] and [2"] in the solid state, with excitation at 254 nm.
2''
2'
2
1.9
1.2
1.0
0.8
0.6
0.4
0.2
0.0
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
1
3
2
mpda
300
400
500
600
700
800
200
300
400
500
600
700
800
wavelength(nm)
wavelength(nm)
Fig. 5. (a) UV–vis spectrogram of compounds [1], [2], and [3] and free ligand in the solid state. (b) UV–vis spectrogram of compounds [2], [20] and doped compound [2"] in
the solid state.
and b, the photoluminescence (PL) is heavily dependent on the
identity of the solvent molecule. For compound [1], the solvents
exhibit varying degrees of quenching effects. Acetone has the
1.0
2
1
most significant influence on the luminescence intensity (Fig. 7a),
which disappeared when complex [1] was immersed in pure
acetone. As for compound [2], luminescence intensity also
disappeared when the compound was immersed in pure
acetone (Fig. 7b). Luminescence intensity was enhanced when
compound [2] was added to DMA or tert-butyl alcohol compared
to other solvents. From Fig. S4a and b we find that compounds [2]
and [20] are also completely quenched by acetone. The result is
consistent with the paper by Li [23], which ascribed fluorescence
quenching to the energy transfer through O–H/O hydrogen-
bonding interactions between coordinated water molecules
(by O–H bonds) and acetone solvent molecules. We believe this
conclusion can explain our results. Such solvent-dependent lumi-
nescence properties are very interesting for the selective sensing
of acetone.
3
0.9
0.8
0.7
0.6
0.5
0
100
200
300
400
500
600
700
800
Temperature(deg)
Fig. 6. Thermogravimetric analysis of compounds [1], [2], and [3].
3.6. Detection of solvent molecules
3.7. Detection for metal ions
To examine the potential of [1] or [2] for sensing of small
molecules, compound [1] or [2] was immersed in different organic
solvent emulsions for luminescence studies. As shown in Fig. 7a
To examine the potential of [1] and [2] for the sensing of metal
ions through cation exchange, the as-synthesized compound [1] or

44
Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
400
380
360
tertButanol
650
600
550
500
450
400
350
300
250
200
150
100
50
CHCN
340
EtOH
320
300
280
260
240
220
200
180
160
140
120
100
80
CH2Cl2
MeOH
DMF
DMA
THF
acetone
60
40
20
0
-50
0
200
300
400
500
600
700
800
tert-ButanolDMF DMA EtOH MeOH THF acetone CH2Cl2 CHCN
wavelength(nm)
400
380
360
340
320
300
280
260
240
220
200
180
160
140
120
100
80
DMA
tertButanol
DMF
CHCN
THF
500
450
400
350
300
250
200
150
100
50
CH2Cl2
MeOH
EtOH
acetone
60
40
20
0
-50
0
200
300
400
500
600
700
800
shudingchunDMF DMA EtOH MeOH THF acetone CH2Cl2 CHCN
wavelength(nm)
Fig. 7. The luminescence spectra of (a) compound [1], (c) compound [2], introduced into various pure solvents when excited at 300 nm. (d) The luminescence intensities of
(b) compound [1], (d) compound [2] in the presence of different pure solvents.
[2] was ground and suspended in DMF solution containing
different metal ions (Zn2þ, Cd2þ, Pb2þ, Fe3þ, Ni2þ, Al3þ, Co2þ
further (Fig. 8e). The luminescent intensity went through a
minimum as a function of Zn2þ concentration. At 4 and 10 mg/ml,
intensity exceeded that of [1] alone. At intermediate concentrations,
(20 and 40 mg/ml), intensities are lower than in the original sample.
Finally, the intensity at 60 mg/ml is the highest of all. Fig. 8f shows
the luminescence response of [2] to Ni2þ ions. The emission
intensity progressively decreased as the concentrations of Ni2þ
increased from 1.25 to 60 mg/mL. When the concentration of Ni2þ
was less than 5 mg/mL, fluorescence intensity was stronger than at
0 mg/mL. The highest intensity is observed when the concentration
,
Agþ, Bi3þ or Ce3þ). The luminescent properties are shown in
Fig. 8a and c. Most metal ions strongly quench the luminescence
intensity. Relative fluorescence intensities are shown in Fig. 8b and
d. For [1], the luminescence intensity at 430 nm is about half of the
original value when Zn2þ ions are involved, and Fe3þ ions can
almost completely quench the luminescence of [1]. The quenching
percentage is 41% in the presence of Zn2þ, while other metal ions
display insignificant differences from one another, with a quench-
ing percentage of 97% for Al3þ and lower values of quenching
percentage for the other metal ions. In conclusion, [1] is a
potential luminescent sensory material for the selective detection
of Zn2þ ions. In the case of [2], most metal ions strongly quench
the luminescence intensity, except for Cd2þ. Compared with the
pure samples of compound [1] or [2], addition of Ni2þ causes a
blue-shift in the emission bands (inset in Fig. 8a, c). To have a
better understanding of the luminescence response of [1] to Zn2þ
ions, the photoluminescence concentration-dependent emission
spectra for different concentrations of Zn2þ ions were studied
of Ni2þ is 1.25 mg/ml, its molar ratio with blank samples (Ni2þ
:
compound [2]) close to 1:1. The detection limits for fluorescence
sensing of Zn2þ and Ni2þ ions were calculated to be, respectively,
2.2 ꢂ 10ꢁ4 M and 2 ꢂ 10ꢁ4 M [24].
The selectivity of compound [1] for Zn2þ was investigated
through a comparative study of the fluorescence responses to
different metal ions in DMF solutions (Fig. 9a). As expected, [1]þ
Zn2þ shows a strong fluorescence in DMF solution, and its
fluorescence was influenced by the addition of Al3þ, Bi2þ, Pb2þ
,
Fe3þ, Agþ, Ni2þ, Ce2þ, Co2þ and Cd2þ (Fig. 9b). Fluorescence

Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
45
100
80
60
40
20
0
1
400
350
300
250
200
150
100
50
Zn
Cd
Pb
Ni
Fe
Al
Bi
Ce
Co
Ag
0
300
400
500
600
700
800
Compound1 Zn
Cd Pb
Ni
Fe
Ag
Al
Bi
Ce Co
Wavelength(nm)
2
Al
Ag
Bi
100
180
160
140
120
100
80
Cd
Ce
Fe
Ni
Pb
Zn
Co
80
60
40
20
0
60
40
20
0
300
400
500
600
700
800
Compound2 Zn
Cd
Pb
Ni
Fe
Ag
Al
Bi
Ce
Co
Wavelength(nm)
1.25mg/ml
5mg/ml
500
450
400
350
300
250
200
150
100
50
8000
7000
6000
5000
4000
3000
2000
1000
0
0mg/ml
60mg/ml
10mg/ml
4mg/ml
10mg/ml
20mg/ml
30mg/ml
40mg/ml
50mg/ml
60mg/ml
0mg/ml
20mg/ml
40mg/ml
0
-1000
-50
200
300
400
500
600
700
800
200
300
400
500
600
700
800
Wavelength(nm)
wavelength(nm)
Fig. 8. The luminescence responses of (a) compound [1], (c) compound [2] dispersed in DMF with various metal ions, when excited at 300 nm. Luminescence quenching
percentage of (b) compound [1], (d) compound [2] in the presence of different metal ions (each 1.0 ꢂ 10 ꢁ4 M). (e) Concentration-dependent emission spectra of compound
[1] after adding different concentrations of Zn2þ ions (mg/ml) when excited at 300 nm. (f) Concentration-dependent emission spectra of compound [2] after adding different
concentrations of Ni2þ ions (mg/ml) when excited at 300 nm.
quenching was detected upon the addition of Fe3þ with Zn2þ. Other
metals also quenched the fluorescence to some extent. Interestingly,
the combination of Zn2 þ þBi2 þ shows a strong fluorescence
emission peak.
3.8. Stability affected by solvents and metal ions
Powder XRD was employed to study the structural stability of
compound [1] or [2] before and after immersion in different

46
Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
32
1+Mn+
1+Mn++Zn2+
30
Compound1
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
1+Zn2+
28
Bi3++Zn2+
26
Ag++Zn2+
24
Ni2++Zn2+
22
Co2++Zn2+
20
Ce3++Zn2+
18
Cd2++Zn2+
16
Pb2++Zn2+
14
Al3+ + Zn2+
12
Fe3++Zn2+
10
8
6
4
2
-1000
0
200
300
400
500
600
700
800
Cd
Pb
Ni
Fe
Ag
Al
Bi
Ce
Co
Wavelength(nm)
Fig. 9. (a) Fluorescence spectra of compound [1] in the presence of various metal ions with Zn2þ. (b) Relative fluorescence intensity of compound [1] (5 mg/ml) in the
presence of various metal ions alone (1.0 ꢂ 10ꢁ4 M, black) and interfering ions with Zn2þ(1.0 ꢂ 10ꢁ4 M, red). (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
300000
250000
after immersed in Zn2+ solution
after immersed in Zn2+ solution
before immersed
200000
150000
100000
50000
0
before immersed
0
10
20
30
40
50
60
0
10
20
30
40
50
60
2θ/deg
2θ/deg
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
after 2 immersed in Ag2+ solution
before 2 immersed in Ag1+ solution
after 1 immersed in Ag1+ solution
before 1 immersed in Ag1+ solution
40000
35000
30000
25000
20000
15000
10000
5000
left
right
before immersed
after immersed in Zn2+ solution
0
0
-5000
0
10
20
30
40
50
60
0
10
20
30
40
50
60
2θ/deg
2θ/deg
Fig. 10. Powder X-ray diffraction profiles of compound [1] before and after immersion in DMF solutions with different metal ions (a), Zn2þ, (b) Fe3þ, (c) Ni2þ for 1 day.
(d) X-ray diffraction profiles of compounds [1] and [2] after immersion in DMF solution containing Agþ for 1 day.

Y. Xiao et al. / Journal of Solid State Chemistry 221 (2015) 37–48
47
Fig. 12. The truth table and logic diagram for the simultaneous monitoring of Zn2þ
and Bi2þ
Fig. 11. The truth table and logic diagram for the simultaneous monitoring of Zn2þ
and Fe3þ
.
.
solvents and in DMF solutions of different ions. From Fig. 10a we
can find that Zn2þ ion did not change the crystal structure of
compound [1]. Some XRD peaks of compound [1] disappeared
with the addition of Fe3þ (Fig. 10b). The result suggests that Fe3þ
may cause the collapse of the crystal structure [25]. With the
addition of Ni2þ ions, we found that the positions of XRD peaks
were shifted slightly (Fig. 10c), which may be attributable to ion
exchange between Ni2þ and Zn2þ [26]. Fig. 10d shows that when
compound [1] or [2] is immersed in Agþ solution, the XRD
patterns change somewhat, suggesting the occurrence of struc-
tural changes. Other data can be found in supporting materials
(Figs. S5–S8). The powder XRD patterns of the compounds soaked
in different solvents and DMF solutions of different ions are similar
to those of the original compounds, suggesting that the basic
frameworks remain the same in these cases. In conclusion,
although the ions will cause the fluorescence quenching of DMF
suspension of compound [1], the mechanisms are different. While
Zn2þ did not damage the structure of the framework, the quantity
of free ions affects the fluorescence intensity. The addition of Fe3þ
destroyed the framework structure and may have generated a
non-fluorescent complex of iron. Exposure to Ni2þ and Agþ may
have generated new materials by ion exchange with the original
compounds, and resulted in a change of fluorescence.
inorganic connectivity built from face-sharing PrO10 polyhedra
with CHOO- acting as M–O–M bridges. [Mn2(mpda)2 (H2O)4] [3] is
a 1-D coordination polymer built from point-sharing MnO6 poly-
hedra. The luminescence study shows that the compounds [1] and
[2] exhibit a very high quenching effect with acetone, making
them promising for use as a luminescent probe of acetone. And [1]
and [2] are potential luminescent selective materials for the
detection of Zn2þ or Ni2þ ions, respectively. Two logic gates have
been constructed using compound 1 where cations (Fe3þ and
Zn2þ, Bi2þ and Zn2þ) act as two inputs.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21371060, 51073061, and
21174044).
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.jssc.2014.09.015.
3.9. Logic gate behavior of [1]
References
The fluorescence properties (output) of compound [1] caused
by chemical input information can be interpreted within the
framework of molecular logic. The low output values (fluorescence
intensity quenched) are translated into binary “0”, while the
strong fluorescence output values correspond to binary “1”, in
accordance with a positive logic convention.
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