Construction of monomers and chains assembled by 3d/4f metals and 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine

Article abstract of DOI:10.1016/j.jssc.2012.07.002

A series of transition metal and lanthanide complexes of 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine (HL, 1), namely [M(L)₂]·5H₂O (M=Ni, 2; Co, 3), [Zn(L) ₂]_n·0.5nH₂O (4) and [Ln(L) ₃]_n (Ln=Nd, 5; Gd, 6; Er, 7) were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Isomorphic compounds 2 and 3 are mononuclear molecules with two ligand chelating to the metal centers via tridentate terpyridyl, while compound 4 adopts 1D chain-like structure, in which five-coordinate zinc centers are surrounded by three ligands. Compounds 5-7 also display 1D chain-like structure, but the nine-coordinate lanthanide centers bonded by four ligands. Luminescent property indicates that compound 4 exhibits photoluminescence in the solid state at room temperature.

Full text of DOI:10.1016/j.jssc.2012.07.002

Journal of Solid State Chemistry 196 (2012) 398–403
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Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Construction of monomers and chains assembled by 3d/4f metals and
40-(4-carboxyphenyl)-2,20:60,200-terpyridine
Juan Yang, Rui-Xiang Hu, Man-Bo Zhang n
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education), College of Chemistry and Chemical Engineering, Hunan Normal University,
Changsha 410081, PR China
a r t i c l e i n f o
a b s t r a c t
A series of transition metal and lanthanide complexes of 40-(4-carboxyphenyl)-2,20:60,200-terpyridine
(HL, 1), namely [M(L)2] ꢀ 5H2O (M¼Ni, 2; Co, 3), [Zn(L)2]n ꢀ 0.5nH2O (4) and [Ln(L)3]n (Ln¼Nd, 5; Gd, 6;
Er, 7) were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffrac-
tion. Isomorphic compounds 2 and 3 are mononuclear molecules with two ligand chelating to the metal
centers via tridentate terpyridyl, while compound 4 adopts 1D chain-like structure, in which five-
coordinate zinc centers are surrounded by three ligands. Compounds 5–7 also display 1D chain-like
structure, but the nine-coordinate lanthanide centers bonded by four ligands. Luminescent property
indicates that compound 4 exhibits photoluminescence in the solid state at room temperature.
& 2012 Elsevier Inc. All rights reserved.
Article history:
Received 22 March 2012
Received in revised form
27 June 2012
Accepted 1 July 2012
Available online 13 July 2012
Keywords:
40-(4-carboxyphenyl)-2,20:60200-terpyridine
Lanthanide
Transition metal
1. Introduction
six-coordination transition metals. Therefore, to further investi-
gate the effect of substituted linear ligands on the structure and
The rational synthesis of metal-organic frameworks (MOFs)
with specified structures and properties is an important aim for
chemists [1–4]. We know that the resultant structure and
physicochemical properties of MOFs largely depend on two key
elements, center atoms and organic ligands [5,6]. Therefore, many
target MOFs by judicious of metal atoms and tailored ligands have
been successfully synthesized [7–10]. Terpyridine derivatives are
important functional ligands for their tunable photophysical and
electrochemical properties. In recent decades, the investigation
on terpyridine derivatives, with the aim of exploring the potential
utility ranging from catalysis to dye-sensitized solar cells, have
been carried out widely [11–19]. Among these derivatives, ter-
pyridine bearing carboxylate function, such as 40-(4-carboxyphe-
property of resultant coordination polymers, we reacted 40-(4-
carboxyphenyl)-2,20:60,200-terpyridine to transition metal and
lanthanide salts, and obtained a series of novel metal compounds:
[M(L)2] ꢀ 5H2O (M¼Ni, 2; Co, 3), [Zn(L)2]n ꢀ 0.5nH2O (4) and
[Ln(L)3]n (Ln¼Nd, 5; Gd, 6; Er, 7).
2. Experimental section
2.1. Materials and measurements
Aqueous solution of Ln(NO3)3 was made by dissolving Ln2O3 in
an appropriate amount of nitric acid. All other reagents and
solvents employed were commercially available and used without
further purification. IR spectra were measured as KBr pellets on a
NICOLET-Avatar 37 in the range 400–4000 cmꢁ1. Thermalgravi-
metric data were collected on a NETZSCH-STA409PC analyzer in
flowing nitrogen at a heating rate of 10 1C/min. Luminescence
spectrum was recorded by using a HitaChi-4500 spectrometer.
The photoluminescence quantum yields were measured by
Edingburgh Instruments FLS920.
nyl)-2,20:60,200-terpyridine
[20–24],
2,20:60,200-terpyridine-40-
carboxylate [25–27] and 4,40,400-tricarboxy-2,20:60,200-terpyridine
[28–30], are perfect multidentate ligands to form novel com-
plexes with intriguing architectures, and as well as a suitable
anchorage on TiO2 for electron injection. In our continuing
investigation on MOFs of linear N-containing carboxylate ligand
[31–35], we find 40-(4-carboxyphenyl)-2,20:60,200-terpyridine (HL),
showing structural similarity to the linear 4-(4-pyridyl)benzoate
and featuring a tridentate terpyridyl and a carboxylate group set
on opposite direction of benzene ring, are potential ‘‘expanded
ligands’’ with typical scaffolds of {M(tyba)2} as bond to some
2.2. Preparation
2.2.1. 40-(4-carboxyphenyl)-2,20:60,200-terpyridine (1)
Powder sample of 40-(4-carboxyphenyl)-2,20:60,200-terpyridine
is synthesized according to the literature procedure [29,36], while
its crystals were prepared by mixing the powder of HL (0.110 g,
n Corresponding author. Fax: þ86 731 88872531.
E-mail address: zmb@hunnu.edu.cn (M.-B. Zhang).
0022-4596/$ - see front matter & 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jssc.2012.07.002

J. Yang et al. / Journal of Solid State Chemistry 196 (2012) 398–403
399
Table 1
Crystallographic data and structure refinement for compounds 1–7.
Compound
1
2
3
4
5
6
7
CCDC code
Formula
Mr
871512
871517
C44H38NiN6O9
853.51
871513
C44H38CoN6O9
853.73
871518
871516
871515
871514
C22H15N3O2
C44H29ZnN6O4.5
779.10
C66H42NdN9O6
1201.33
C66H42GdN9O6
1214.34
296(2)
C66H4ErN9O6
1224.35
296(2)
353.37
T (K)
153(2)
153(2)
153(2)
293(2)
296(2)
Crystal system
Space group
Monoclinic
P2(1)/c
Triclinic
P-1
Triclinic
P-1
Monoclinic
C2/c
Monoclinic
C2/c
Monoclinic
C2/c
Monoclinic
C2/c
10.194(2)
8.7035(17)
8.7440(17)
33.088(7)
33.8052(6)
33.812(7)
33.794(4)
˚
a (A)
7.1491(14)
22.340(5)
13.502(3)
16.591(3)
14.494(3)
16.430(3)
10.035(2)
24.697(5)
13.9956(2)
12.1766(2
13.872(3)
12.253(3)
13.7643(16)
12.2604(14)
˚
b (A)
˚
c (A)
a
b
g
(1)
(1)
(1)
90.00
93.16(3)
97.45(3)
91.07(3)
1929.7(7)
93.52(3)
97.26(3)
91.24(3)
2060.8(7)
90.00
90.00
90.00
90.00
90.56(3)
90.00
119.12(3)
90.00
108.7210(10)
90.00
108.978(2)
90.00
109.2080(10)
90.00
3
1627.9(6)
7164(2)
5456.24(15)
5435(2)
5385.5(11)
˚
V (A )
Z
4
2
2
8
4
4
4
F (0 0 0)
Dc (g cmꢁ3
736
888
886
3208
1.445
0.742
1.069
0.0473
0.0994
2436
1.462
1.016
1.039
0.0364
0.0717
2452
1.484
1.285
1.003
0.0191
0.0501
2468
1.510
1.623
1.030
0.0276
0.0576
)
1.442
0.095
1.036
0.0492
0.1160
1.469
0.571
1.082
0.0495
0.1211
1.376
0.480
0.955
0.0512
0.1363
m
(mmꢁ1
)
GOF on F2
R1 [I42
(I)]a
(I)]b
s
wR2 [I42
s
a
R1¼
S
(9Fo9ꢁ9Fc9)/
S
9Fo9.
b
wR2¼{
S
[w(Fo2ꢁFc2)2]/ [w(Fo2)2]}1/2
S .
0.3125 mmol) with silver nitrate (0.021 g, 0.125 mmol) in 5 mL
distilled water and heating at 180 1C for 7 day. Yield: 42%, based
on HL. Main IR absorption bands (cmꢁ1): 3448.29(w), 1703.88(s),
1588.24(v), 1471.92(s), 1264.96(sh), 857.67(w), 772.25(m),
733.72(w), 694.50(w).
2.2.6. Synthesis of [Gd(L)3]n (6)
Compound 6 was prepared by a similar procedure to that of 5
except that Nd(NO3)3 was replaced by Gd(NO3)3 (0.125 mmol,
1.25 mL). Light brown plate crystals of 6 were collected (yield:
40%, based on Gd). Main IR absorption bands (cmꢁ1): 3429.83(w),
1584.46(b), 1549.34(b), 1409.70(s), 819.18(b), 784.10(s).
2.2.2. Synthesis of [Ni(L)2]n ꢀ 5H2O (2)
2.2.7. Synthesis of [Er(L)3]n (7)
A
mixture of Ni(OAc)2 ꢀ 4H2O (0.031 g, 0.125 mmol), HL
Compound 7 was prepared by a similar procedure to that of 5
except that Nd(NO3)3 was replaced by Er(NO3)3 (0.125 mmol,
1.25 mL). Light brown plate crystals of 7 were collected (yield:
39%, based on Er). Main IR absorption bands (cmꢁ1): 2924.60(b),
1592.93(w), 1551.03(w), 1418.89(s), 819.08(b), 783.43(s).
(0.088 g, 0.25 mmol) in deionized water (5 mL) was adjusted to
pH¼11.0 with triethylamine, and sealed in a 28 mL Teflon-lined
stainless steel vessel, which was heated at 180 1C for 7 day under
autogenous pressure and thereafter cooled to room temperature.
Brown block crystals of 2 were collected after washing with
distilled water and dried in air (yield: 49%, based on Ni). Main IR
absorption bands (KBr, cmꢁ1): 3437.42(b), 1605.07(s), 1552.90(s),
1367.78(s), 786.42(s).
2.3. X-ray crystallography
Suitable single crystals were selected and mounted on a glass
fiber. The Data of 1–4 were collected on a Bruker P4 CCD, 5 on
2.2.3. Synthesis of [Co(L)2]n ꢀ 5H2O (3)
SADABS-2008/1-Bruker AXS and 6–7 on SMART APEX II area detec-
˚
Compound 3 was synthesized by a similar procedure to that
of 2 except that Ni(OAc)2 ꢀ 4H2O was replaced by Co(OAc)2 ꢀ 4H2O
(0.031 g, 0.125 mmol), a large quantity of black plate crystals were
obtained (yield: 64%, based on Co). Main IR absorption bands (KBr,
cmꢁ1): 3209.33(b), 1605.73(s), 1553.79(s), 1367.72(s), 787.33(s).
tors with graphite-monochromated Mo K radiation (
l¼0.71073 A).
a
All structures were solved by direct method and refined on F2 by full-
matrix least-squares methods using the SHEXTL 97 program package
[37,38]. All non-hydrogen atoms were refined anisotropically. The
positions of hydrogen atoms on organic ligands were generated
geometrically and allowed to ride on their parent atoms. While the
hydrogen atoms associated with the lattice water molecules (O6, O7
and O8) were not located from the difference Fourier maps because
they were disordered across two positions each. The crystallographic
data are summarized in Table 1, and selected bond lengths are listed
in Table S1 (see in Supporting materials). Crystallographic data
(excluding structure factors) for compounds 1–7 in this paper have
been deposited with Cambridge Crystallographic Data Center, CCDC
reference number 871512–871518.
2.2.4. Synthesis of [Zn(L)2]n ꢀ 0.5nH2O (4)
Compound 4 was synthesized by a similar procedure to that of 2
except that Ni(OAc)2 ꢀ 4H2O was replaced by Zn(OAc)2 ꢀ 2H2O
(0.027 g, 0.125 mmol). Yellow prism crystals were obtained (yield:
52%, based on Zn). Main IR absorption bands (KBr, cmꢁ1):
3054.91(w), 1612.64(s), 1565.31(w), 1363.20(s), 785.09(s).
2.2.5. Synthesis of [Nd(L)3]n (5)
Compound 5 is hydrothermally synthesized by mixing 0.1 M
Nd(NO3)3 solution (0.125 mmol, 1.25 mL). HL (1 mmol, 374 mg),
and deionized water (8 mL) in a 28 mL Teflon-lined stainless steel
vessel and heated at 180 1C for 6 day and then cooled to room
temperature. Light brown plate crystals of 5 were collected after
washing with distilled water and dried in air (yield: 37%, based on
Nd). Main IR absorption bands (cmꢁ1): 3427.40(w), 1583.92(s),
1547.68(s), 1406.72(s), 817.83(b), 783.85(s).
3. Results and discussion
3.1. Syntheses
Our original idea is to synthesize some novel 3d–4f hetero-
metallic coordination polymers by using 40-(4-carboxyphenyl)-2,20:60,

400
J. Yang et al. / Journal of Solid State Chemistry 196 (2012) 398–403
200-terpyridine as ligand based on following consideration: (1) The
linear -substituted pyridinecarboxylate, such as isonictonate [39,40]
g
and 4-(4-pyridyl)benzoate [41], are perfect N,O-donating ligands to
capture 3d and 4f ions simultaneously and to construct some
heterometallic extend networks effectively. 40-(4-carboxyphenyl)-
2,20:60,200-terpyridine, with a tridentate terpyridyl and a carboxylate
group setting on opposite direction of benzene ring, maybe show
some structure and coordination similarity to the linear g-substitut ed
pyridinecarboxylate. (2) The 40-(4-carboxyphenyl)-2,20:60,200-terpyri-
dine prefers to bond transition metal ions through the terpyrdyl but
leave carboxylate group uncoordination to form {M(L)2} scaffold,
which can serve as potential expanded spacers as further assemble
with lanthanide or other transition metal ions. (3) The compounds
of 40-(4-carboxyphenyl)-2,20:60,200-terpyridine are potential lumines-
cent materials because the delocalized
p-electron terpyridyl is a
strongly absorbing chromophoric group. At first, we carried out the
synthesis by mixing the first transition series of Zn, Ni, Co, Cu, and Fe
with HL, and obtained title compounds of 2–4. Then, we further
explored the assembly of HL with Ru and Cd salts, respectively,
isomorphic compounds of [Ru(L)2]ꢀ 5H2O [27] and [Cd(L)2]n ꢀ nH2O
were obtained [22]. At the same time, we investigated the reaction
between lanthanide ions and HL, crystal samples of 5–7 were
appeared [24].
3.2. Description of the crystal structures
Scheme 1. Coordination modes of 40-(4-carboxyphenyl)-2,20:60,200-terpyridine in
2–7.
3.2.1. Structure of 40-(4-carboxyphenyl)-2,20:60,200-terpyridine (1)
In compound 1, the asymmetric unit contains one 40-(4-
carboxyphenyl)-2,20:60,200-terpyridine molecule. The bond lengths
and angles of four aromatic rings are in normal range, and the
three pyridyl ring is coplanar with a trans-trans-trans configura-
tion (Fig. S1, see in Supporting materials). Adjacent two molecules
connect with each other via hydrogen bonds O(2)–H(2B)yN(3) to
form the dimer expanding in [2 1 0] or [ꢁ2 1 0] direction (Fig. S2),
then the dimers of same direction interact with each other and
give rise to supermolecular chains via weak p–p stacking, and the
˚
perpendicular distance between the dimers is 3.4179 A.
3.2.2. Structure of [M(L)2] ꢀ 5H2O (M¼Ni, 2; Co, 3)
Compounds 2 and 3 are isomorphic to ruthenium (II) complex
of 40-(4-carboxyphenyl)- 2,20:60,200-terpyridine reported by Con-
stable et al. (Fig. S3) [27]. The asymmetric unit of 2 comprises one
Ni(II) atom, two L ligands, and five lattice water molecules (Fig. 1).
Each Ni(II) center is six-coordinated by six nitrogen atoms from
two ligands and leave carboxylate group uncoordination
(Scheme 1a). Three pyridyl rings in cis-cis-cis terpyridyl are nearly
coplanar. In the structures of 2 and 3, Ni–N distances vary from
Fig. 2. ORTEP view of 4 with 50% thermal ellipsoids.
is five-coordinated by three nitrogen atoms and two oxygen
atoms from three ligands. The Zn–O and Zn–N distances fall in
the normal range [42,43]. In 4, the two crystallographically
independent 40-(4-carboxyphenyl)-2,20:60,200-terpyridine present
-1k3N,N0,N00:2 1O links
two types of coordination modes: m2-L k
two Zn(II) ions through the tridentate chelating terpyridyl and
˚
1.9888(17) to 2.1149(19) A, while the Co–N distances range from
˚
1.877(2) to 2.163(2) A. The monomeric molecules stretch along c
axis forming a potential expand spacer.
3.2.3. Structure of [Zn(L)2]n ꢀ 0.5nH2O (4)
As shown in Fig. 2, the asymmetric unit of compound
4 comprises one Zn(II) atom, and two L ligands. The Zn(II) center
monodentate carboxylate to form one-dimensional chain along c
axis (Scheme 1b, Fig. 3a); and L-
k2O,O0 just serves as terminal
ligand to complete the coordination sphere of Zn(II) center via
the bidentate chelating carboxylate group bonding to Zn(II)
but leave the trans-trans-trans terpyridyl uncoordination
(Scheme 1c). the terminal ligands on the chain stretch in two
directions with an angle of about 901 but not the 1801 as
reported in [Cd(tyba)2]n ꢀ nH2O. In addition, It is worthwhile to
mention that the chain structure of 4 is also different from
double chain structure of [Cd(tyba)2]n ꢀ nH2O, in which the Cd(II)
center is seven-coordinated and the bridging ligand adopts m2
k3N,N0,N00:2k2O,O0 coordination mode. Finally, the chains pack
with–ABAB-mode along a axis (Fig. 3b).
-L-
1
Fig. 1. ORTEP view of 2 with 50% thermal ellipsoids.

J. Yang et al. / Journal of Solid State Chemistry 196 (2012) 398–403
401
Fig. 5. View of 1D chain structure of compound 5.
Scheme 2. Synthetic pathway of the compounds 1–7.
N4A). The m2-L
-1k3N,N0,N00:2k2O,O0 connects two Nd(III) centers
via bidentate chelating carboxylate and tridentate terpyridyl of
Fig. 3. View of (a) the chain structure along b axis and (b) the chains stacking
cis-cis-cis configuration to form a 1D chain along b axis, while the
L
-1k2O,O0 coordinate to the Nd(III) center through bidentate
mode in 4.
chelating carboxylate and set on the opposite sides of the chain
(Fig. 5). Then, adjacent chains connect each other via two types of
p
–
p
stacking interactions,
p
(C1–C5, N1) ꢀ ꢀ ꢀ
p
(C6D–C7D, N2D)
˚
(D¼x, 2ꢁy, 1/2þz), centroid–centroid distance¼4.2212 A, face
˚
distance¼3.6235 A, dihedral angle¼24.7561 and
p(C6–C10, N2)
ꢀ ꢀ ꢀ p(C6E–C10E, N2E) (E¼1/2ꢁx, 1/2ꢁy, z), centroid–centroid
distance¼3.6552, to form the 3-D supramolecular network (Fig.
S4). Isomorphic compounds 6 and 7 exhibit similar structural
features to that of 4 (Fig. S5).
From above discussion, we can find that the radius of metal
centers and electron configuration play key role in the structure
of title compounds: for 2 or 3, the six-coordinated Ni(II) or the
Co(II) ion has larger radius than Zn(II), and exists in the octahedral
geometrical environment; for 4, the smaller radius of Zn(II) ion
will produce greater tension for the coordination of terpyridyl
(the angle of N1–Zn1–N3 is 150.751, that of N1–Ni–N3 is 155.971),
which force other ligands to abandon same coordination behavior
as bonding to the metal; for 5, the larger radii of lanthanide ions
permit more 40-(4-carboxyphenyl)-2,20:60,200-terpyridine to
appear in the coordination space, which further effect the linkage
of resultant framework (Scheme 2).
Fig. 4. ORTEP view of 5 with 50% thermal ellipsoids.
3.2.4. Structure of [Ln(L)3]n (Ln¼Nd, 5; Gd, 6; Er, 7)
X-ray analysis reveals that 5–7 are isomorphous compounds
crystallizing in the monoclinic space group C2/c. The asymmetric
unit of 5 contains half Nd(III) ion and one and a half L anions.
Nd(III) center is nine-coordinated by three nitrogen atoms of
terpyridyl and six oxygen atoms from three ligands (Fig. 4). The
3.3. IR spectroscopy and thermal stability analysis
In compounds 2–7, the characteristic features of 40-(4-carbox-
yphenyl)-2,20:60,200-terpyridine dominate the IR spectrum, in
which the absence of any strong bands around 1700 cmꢁ1
indicates that 40-(4-carboxyphenyl)-2,20:60,200-terpyridine are
deprotonated. The medium intensity peaks around 1600 cmꢁ1
can be attributed to the characteristic stretching vibration of
pyridine and benzene rings, while those appearing at about 1550
and 1450 cmꢁ1 are asymmetric and symmetric stretching vibra-
tions of –COOꢁ. As for compound 1, the sharp peak at 1703 cmꢁ1
shows the stretching vibration of protonated –COOH (Fig. S6).
˚
average bond length of Nd–N 2.5826 A is longer than that of Nd–O
0
0
0
00
˚
2.4951 A. In 5, 4 -(4-carboxyphenyl)-2,2 :6 ,2 -terpyridine dis-
plays two types of coordination mode, m2
-1k3N,N0,N00:2k2O,O0
and
-1k2O,O0, with all the bond lengths of four aromatic rings are
in normal range (Schemes 1c and d). the cis-cis-cis terpyridyl of
-1k3N,N0,N00:2k2O,O0 are noncoplanar with a dihedral angle
-L
L
m2
-L
about 25.131 between two side pyridine ring (C1–C5, N1) and
(C11–C15, N3), and the dihedral angle of the trans-trans-tans
terpyridyl of
L
-1k2O,O0 is about 17.671 between the ring of (C23–
C27, N4) and its symmetrical generated ring of (C23A–C27A,

402
J. Yang et al. / Journal of Solid State Chemistry 196 (2012) 398–403
4. Conclusions
In conclusion, we have prepared a series of monomers and
chains constructed by 3d or 4f metals with 40-(4-carboxyphenyl)-
2,20:60,200-terpyridine. The assembly of Ni(II), Co(II) or Zn(II) ions
with the ligand gives rise to discrete monomers for Ni(II) and
Co(II), and chain-like polymer for Zn(II). The structural variability
between them results from the differences of ionic radii and
electron configuration of metal centers. For the same reason,
lanthanide compounds present other chain structure with the
metal centers surrounded by four 40-(4-carboxyphenyl)-2,20:60,200-
terpyridine. The monomeric molecules of 2 and 3 are potential
expand spacer to construct some extend polymers as the uncoor-
dination carboxylate further bond to other metal centers, such as
lanthanide ions.
Acknowledgments
Fig. 6. The emission spectra of HL and compound 4.
This work was financially supported by National Natural
Science Foundation of China (No. 20871046), Program for Excel-
lent Talents in Hunan Normal University (No. ET20903), and
Scientific Research Fund of Hunan Provincial Education Department
(No. 11B077).
The thermal stabilities of compounds 2–4 were examined
through TG analyses in dry nitrogen atmosphere from 25 to
800 1C (Fig. S7). In the TGA curve of complex 2, the first weight
loss of 11.13% from 25 to 343 1C corresponds to the loss of five
lattice water molecules, which is in good agreement with the
calculated value (10.54%). The second weight loss from 343 to
799 1C corresponds to the decomposition of two 40-(4-carboxy-
phenyl)-2,20:60,200-terpyridine (obsd. 42.85% calcd. 41.28%). Com-
plex 4 undergoes three main steps of weight losses. The first loss
of 2.40% from 25 to 391 1C corresponds to the lattice water
molecule (calcd. 1.16%). On further heating from 391 to 479 1C,
the framework begins to break gradually with a weight loss of
45.07%, which corresponds to the decomposition of one 40-(4-
carboxyphenyl)-2,20:60,200-terpyridine ligand (45.28%). The final
step corresponds to that of the second ligand. By comparison, we
see that the polymeric 4 is more stable than monomeric 2. The
reason can be illustrate by the different coordination modes of
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.2012.07.
002.
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