Syntheses and characterization of two novel 1D Pb(II) Halide supramolecular polymers possessing incomplete Cubane subunit directed by π-conjugated Dication templates

Article abstract of DOI:10.1007/s12039-015-0892-0

Two novel cation-templated complexes, {(1, 4-PMBP)[Pb₄I₁₀] DMF}_n(1) {(DBBP)₂[Pb₅I₈Br₆]}_n(2), (1, 4-PMBP 2Br =1, 1"-[1, 4-phenylene-bis(methylene)]bis-4, 4'-bipyridiniu

Full text of DOI:10.1007/s12039-015-0892-0

J. Chem. Sci. Vol. 127, No. 7, July 2015, pp. 1235–1242. ꢀc Indian Academy of Sciences.
DOI 10.1007/s12039-015-0892-0
Syntheses and characterization of two novel 1D Pb(II) Halide
supramolecular polymers possessing incomplete Cubane subunit
directed by π-conjugated Dication templates
a
b
a
a
a
a
CHENGJIE MA , MEI LIU , WENLI ZHANG , HAIJUAN DU , YAO LI , CHAOHAI WANG
a,∗
and YUNYIN NIU
a
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China
Physical, Chemical and Biological Department, Henan Jiaozuo Teacher’s College, Jiaozuo 454000, P. R.
b
China
e-mail: niuyy@zzu.edu.cn
MS received 26 January 2015; revised 25 March 2015; accepted 28 March 2015
Abstract. Two novel cation-templated complexes, {(1, 4-PMBP)[Pb4I10]·DMF} n(1) {(DBBP)2[Pb5I8Br6]}
n(2), (1,4-PMBP·2Br =1,1”-[1,4-phenylene-bis(methylene)]bis-4,4’-bipyridinium dibromide; DBBP·2Br = N,
N’-dibenzyl- 4, 4’-bipyridinium dibromide) have been synthesized via the self-assembly reaction in solution.
X-ray crystallography showed that compounds 1 and 2 can be regarded as 1D iodoplumbate examples which
contain incomplete cubane subunit directed by π-conjugated dication templates. It is the H-bonds and electro-
static interactions between the organic counter cations and inorganic moieties that contribute the crystal pack-
ing. These compounds have been further characterized by IR spectroscopy, UV-Vis spectra, elemental analysis
and thermostability properties.
Keywords. π-conjugated cation templates; iodoplumbates hybrids; inorganic/organic interactions.
2
−
18–20
2n−
1
. Introduction
(PbCl ) , (PbCl )
and 3-D frameworks [Pb7I18]
4
3
4
− 21
and [Pb I (dmf) ] .
1
5 34
6
In the last decade, template-oriented organic-inorganic
hybrid materials have gradually become one of the most
actively explored area of chemical engineering and
molecular science because of their fascinating crystal
structures and potential applications in photochromism,
electrical conductivity, biology, catalysis, etc.1 More
and more attention has been drawn to this domain not
only because of the opportunity to combine the distinc-
tive properties of both inorganic and organic compo-
The structural diversity of the haloplumbate-based
hybrid is due to two factors: (i) the coordination
number of Pb ion ranges from 4 to 8 and its coordi-
2+
nation geometry can be distorted tetrahedron, square
pyramid, octahedron, triangular prism, monocapped
–5
22–24
octahedron or bicapped octahedron and so on.
(ii)
stepwise aggregations of the building units with the
above-mentioned coordination geometry give rise to
various anionic structural motif, via sharing of X-X-X
6
nents in one material, but also because of the possi-
−
−
triangular faces, X-X edges or X apexes (X = Cl ,
bility of producing novel properties by the synergetic
−
−
Br or I ion) of the adjacent coordination polyhe-
dra, from the mononuclear or polynuclear species
to higher dimensionality. However, the synthesis of
compounds directed by π-conjugated N-containing
organic dication templates are rarely reported.25 On
the basis of our previous work, subtle changes of
the organic cationic properties, such as size, shape,
and distribution of the positive charge, may lead to
interactions between two counter components.7
Among the various families of inorganic-organic
hybrid polymers, haloplumbates are an important
family of hybrid functional materials.8 The com-
pounds have been reported to exhibit rich anion struc-
tures, including discrete 0-D oligomers: mononuclear
2
−
2−
4−
(
PbI ) , binuclear (Pb I ) , trinuclear (Pb I ) , pen-
4 2 6
3 10
10−
6
−
tanuclear (Pb I ) , hexanuclear (Pb I ) , heptanu-
clear (Pb I ) , decanuclear (Pb I ) , and octade-
canuclear (Pb I ) clusters;
Pb I ) , and (Pb Cl I ) ;
5
16
−
6 22
26
diverse aggregates of haloplumbate. Recently, we
8
8−
7
22
10 28
found that π-conjugated 4,4’-bipyridine derivative
dication possesses the ideal size for structure-directing
for construction of the organic-inorganic hybrid poly-
mers. So in this contribution, we have selected two
new cation-templates (scheme 1) and successfully
8−
9–13
3−
1-D chains (PbI ) ,
2-D layers (PbI ) ,
1
8 44
5
2
−
2− 14–17
2−
(
2
6
2
2 4
4
∗
For correspondence
1235

1236
Chengjie Ma et al
2. Experimental
+
N
2.1 Materials and Instruments
N
N
N
N
All chemicals and solvents were of A.R. grade and
used without further purification. The FT-IR spectra
were recorded from KBr pellets in the range from 4000
2Br
2Br
−1
to 400 cm on a Bruker VECTOR 22 spectrometer.
Elemental analysis was carried out on a Vario EL III
elemental analyzer(C, H and N). Thermal analyses were
performed on a SDT 2960 thermal analyzer from room
+
N
◦
◦
−1
temperature to 800 C at a heating rate of 5 C min
(a)
(b)
under air flow. Powder X-ray diffraction (Cu Kα radi-
ation, λ =1.5418 Å, 5.08 second per step, 293 K) pat-
terns were collected on an X’Pert PRO diffractometer in
Scheme 1. The molecular structure of the dications (a) 1,
-PMBP·2Br, (b) DBBP·2Br.
4
◦
the scan range of 5–70 . The UV-Vis diffuse reflectance
spectra (DRS) were taken on a Cary 5000 UV-
synthesized two novel complexes which contain incom-
Vis-NIR spectrophotometer with BaSO as reference
plete subunit, {(1, 4-PMBP)[Pb I ]·DMF} (1) {(DBB
4
4
10
n
from 800 to 200 nm. The absorption spectra were
calculated from reflectance spectra using the Kubelka-
P) [Pb I Br ]} (2), (1,4-PMBP·2Br =1,1”-[1,4-pheny-
2
5 8
6
n
lene-bis(methylene)]bis-4,4’-bipyridinium dibromide;
DBBP·2Br = N, N’-dibenzyl- 4, 4’-bipyridinium
dibromide). To the best of our knowledge, compounds
2
Munk function: α/S = (1-R) /2R, where α is the
absorption coefficient, S is the scattering coefficient
(which is practically wavelength independent when the
1
and 2 can be regarded as 1D iodoplumbate examples
particle size was larger than 5 μm), and R is the
reflectance.
which contain incomplete cubane subunits. We have
also investigated the thermal behavior and optical properties.
Table 1. Crystal data and structure refinement details for 1 and 2.
Complexes
1
2
Empirical formula
Formula weight
Crystal system
Space group
a/Å
C31H31I6N5OPb2
1665.39
C48H44Br6I8N4Pb5
3207.48
monoclinic
P21
4.59957(9)
19.5863(4)
21.8372(4)
90.00
95.1329(17)
90.00
1959.39(6)
2
monoclinic
C2/c
27.769(3)
21.1463(8)
15.4603(14)
90.00
130.086(15)
90.00
6945.9(9)
4
b/Å
c/Å
◦
α ( )
◦
β( )
γ ( )
◦
V /Å3
Z
−3
ρ/Mg cm
μ/mm
F(000)
2.823
53.87
1484.0
3.067
55.310
5616.0
−
1
Crystal size/mm
T /K
0.18 × 0.12 × 0.06
0.26 × 0.07 × 0.05
291.15
291.15
Reflections collected
Independent reflections
data/restrains/parameters
14447
12898
ꢀ
ꢀ
7378[R =0.0380, R
= 0.0549]
6215 [R = 0.0423, R
= 0.0481]
sigma
sigma
7378/3/408
1.037
6215/0/321
1.036
2
GOF on F
Final R indices [I>2σ (I)]
R indices (all data)
R1 = 0.0474, wR2 = 0.1174
R1 = 0.0634, wR2 = 0.1734
R1 = 0.0559, wR2 = 0.1261
R1 = 0.0742, wR2 = 0.1873
Largest diff. peak
1.80
−1.16
2.81
−1.32
−3
hole(e Å
)

Pb(II) supramolecule directed by conjugated dications
1237
2
.2 Organic cation template syntheses
2.3 Synthesis of compounds {(1, 4-PMBP)
Pb I ]·DMF} (1) and {(DBBP) [Pb I Br ]} (2)
[
4
10
n
2
5
8
6
n
2
.2a Synthesis of 1,4-PMBP·2Br: 1,4-PMBP·2Br
was prepared by direct alkylation of 4, 4’-dipyridine Compounds 1 and 2 were synthesized similarly. A
with 1, 4-bis(bromomethyl)benzene which were re- methanol solution (0.5 mL) of 1, 4-PMBP· 2Br or
◦
fluxed at 85 for 24 h (acetonitrile served as the solvent DBBP·2Br (0.05 mmol) was added into a stirring light
for the reaction).27 A brown precipitate was obtained yellow solution of PbI (0.05 mmol) dissolved in 5.0
2
and the reaction mixture was cooled to room temper- mL DMF/H2O with excess KI (0.25 mmol). The pre-
ature. It was then filtered off and washed with ace- cipitate formed was dissolved by adding more DMF
tonitrile, and dried under vacuum. Brown powder was (5 mL) until the precipitate disappeared. The yellowish
obtained in 57% yield.
solution was filtered and slowly evaporated in a vial at
room temperature. Two months later, red crystals suit-
2
.2b Synthesis of DBBP·2Br: DBBP·2Br was pre- able for X-ray analysis were obtained in about 48%
pared through Menshutkin reaction by heating the mix- yield (for 1) and 72% (for 2) based on lead ion.
−1
ture of 4,4-bipyridine (3.0 mmol) and benzyl bromide
8.3 mmol) in dry DMF (10 mL) under N gas atmo- 2922.11(w), 2160.92(w), 1647.45(s), 1630.41(s),
IR (KBr, cm ) for 1: 3441.34(m), 3019.80(w),
(
2
◦
sphere (70 C, 24 h). Resulting precipitate was washed 1541.65(m), 1522.00(w), 1487.81(w), 1462.74(w),
with acetone and recrystallized from ethanol to obtain 1428.71(w), 1405.00(m), 1384.03(m), 1345.74(w),
the product as yellow crystals with 84% yield.2
8
1284.54(w), 1239.18(w), 1216.49(w), 1161.15(w),
◦
Table 2. Selected bonds distances (Å) and angles ( ) for compounds 1 and 2.
1
Pb1-I1
Pb1- I3
Pb2-I4
Pb2-I5
Pb1 -I3
I1-Pb1-I2
I1-Pb1-I3
I2 -Pb1-I4
I3- Pb1-I2
I3-Pb1-I3
I4-Pb2-I4
I5-Pb2-I4
I6-Pb2-I4
I6-Pb2-I5
3.085(1)
3.223(1)
3.257(1)
3.201(1)
3.223(1)
93.68(3)
87.36(3)
90.70(3)
89.16(3)
92.15(3)
88.90(3)
88.50(3)
98.87(4)
94.57(4)
Pb1-I2
Pb1-I3
3.296(1)
3.162(1)
3.310(1)
2.968(1)
3.310(1)
94.76(3)
169.61(3)
95.21(3)
177.55(3)
87.40(3)
166.33(3)
87.70(3)
98.17(4)
Pb1-I21
Pb1-I4
Pb2-I5
3.237(1)
3.405(1)
3.207(1)
3.237(1)
3.201(1)
88.42(3)
89.48(3)
177.57(3)
89.13(3)
82.82(3)
166.54(3)
91.74(3)
95.43(4)
1
2
Pb2-I4
Pb2-I6
2
2
Pb1 -I2
2
1
1
Pb2 -I4
Pb2 -I5
1
1
I1-Pb1-I2
I1-Pb1-I4
I2-Pb1-I4
I1-Pb1-I3
1
I2 - Pb1-I2
1
1
I3 - Pb1-I2
1
1
1
I3-Pb1- I2
I3- Pb1-I4
I3 -Pb1-I2
1
1
I3 -Pb1-I4
2
2
2
I5 -Pb2-I4
I5-Pb2-I4
2
2
2
I5 -Pb2-I4
I5 -Pb2-I5
2
2
I6-Pb2-I4
I6-Pb2-I5
2
1
1
Pb1-I1
Pb1-I2
Pb2-I1
Pb2-I4
Pb3-Br1
Pb2 -I1
I1-Pb1-I1
I2-Pb1-I1
I3 -Pb1-I1
I3 -Pb1-I1
I3 -Pb1-I2
I2-Pb2-I1
I4-Pb2-I1
Br1-Pb2-I1
Br1-Pb2-I4
3.327(1)
3.210(1)
3.336(1)
3.148(1)
3.103(1)
3.336(1)
84.77(4)
94.29(3)
171.73(3)
92.25(3)
93.23(3)
87.72(3)
173.60(3)
86.56(4)
87.38(4)
95.41(5)
87.39(4)
Pb1-I1
Pb1-I3
3.327(1)
3.158(1)
3.199(1)
2.936(1)
2.772(2)
3.158(1)
94.29(3)
86.63(3)
92.25(3)
85.91(3)
85.91(3)
176.68(3)
94.33(3)
89.85(4)
172.25(4)
88.09(6)
Pb1-I2
3.210(1)
3.158(1)
3.214(1)
3.249(1)
2.855(1)
3.249(1)
86.62(3)
178.77(5)
171.73(3)
93.23(3)
91.71(4)
91.10(3)
87.18(3)
93.17(4)
92.29(5)
91.96(5)
2
3
Pb1-I3
2
Pb2-I2
Pb2-Br1
Pb3-Br2
Pb2-I3
4
Pb3-I4
Pb3-Br3
2
2
3
Pb1 -I3
Pb3 -I4
I2-Pb1-I1
I2 -Pb1-I2
I3 -Pb1-I1
I3 -Pb1-I2
I3 -Pb1-I3
I3-Pb2-I1
I4-Pb2-I3
Br1-Pb2-I3
1
1
I2 -Pb1-I1
1
1
1
1
I2 -Pb1-I1
2
2
1
3
1
I3 -Pb1-I1
3
2
2
1
3
I3 -Pb1-I2
3
3
1
2
I3 -Pb1-I2
3
3
I2-Pb2-I3
I4-Pb2-I2
Br1-Pb2-I2
Br1-Pb3-I4
Br2-Pb3-Br3
3
3
4
4
Br2-Pb3-I4
Br3-Pb3-I4
4
Br2-Pb3-Br1
Br3-Pb3-Br1
1
2
1
2
3
4
5
symmetry codes: -1+X,+Y,+Z; 1+X,+Y,+Z for 1; -X,+Y,-1/2-Z; -X,1-Y,-Z; +X,1-Y,-1/2+Z; +X,1-Y,1/2+Z; 1/2-
6
X,1/2-Y,-Z; 1-X,+Y,1/2-Z for 2.

1238
Chengjie Ma et al
1
7
6
099.93(w), 1069.56(w), 882.47(w), 813.11(m), thermal parameters. The hydrogen atoms were assigned
67.20(w), 729.30(w), 711.34(w), 622.68(w), with common isotropic displacement factors and
04.12(w), 599.69(w), 512.59(w). Anal. Calcd for included in the final refinement by using geometrical
C H I N OPb : C 22.36, H 1.88, N 4.21%. Found: C constraints. The structures were refined with full-matrix
3
1
31 6
5
2
2
2.18, H 1.76, N 4.11%.
least-squares techniques on F2 using SHELXTL-97.29
−1
IR (KBr, cm ) for 2: 3442.59(s), 3107.81(w), Crystallographic data and structural refinement details
042.11(w), 2924.18(w), 2363.33(w), 2169.50(w), for 1 and 2 were summarized in table 1. Selected bond
735.11(w), 1718.38(w), 1701.03(w), 1653.91(w), lengths and angles of 1–2 were summarized in table 2.
629.15(m), 1558.10(w), 1493.51(w), 1437.43(w),
3
1
1
1
1
6
384.24(m), 1348.61(w), 1268.25(w), 1208.71(w),
154.24(w), 1026.79(w), 806.23(w), 742.04(m),
3
. Results and Discussion
99.79(w). Anal. Calcd for C H Br I N Pb : C 17.97,
48
44
6 8
4
5
H 1.38, N 1.75%. Found: C 17.61, H 1.27, N 1.59%.
3.1 Crystal Structures and Characterization
The X-ray single-crystal structural analysis reveals that
compound 1 crystallizes in the monoclinic system with
the space group P2 The asymmetric unit consists
2
.4 X-Ray Crystallography
1
−
.
2
2+
Crystallographic data for 1 and 2 were collected at of an anion [Pb I ] , one [1,4-PMBP] cation and
4
10
RT on a Bruker APEX-II area detector diffractometer one DMF molecule as shown in figure 1a. Compound
equipped with graphite-monochromated Mo-Kα radia- 1 exhibits a 1D inorganic open-framework structure,
tion (λ = 0.71073 Å). The structures were solved by in which an incomplete cubane chain (ICC) acts as
direct methods and expanded using Fourier techniques. the building block of the inorganic framework. There
Non-hydrogen atoms were refined with anisotropic are two crystallographically independent Pb atoms,
Figure 1. (a) the structural unit of compound 1; (b) the 1D inorganic chains for compound 1 view along
the b axis; (c) The packing diagram of compound 1 view along a axis.

Pb(II) supramolecule directed by conjugated dications
1239
which are all situated in a slightly distorted octahedral I5 atoms as shown in figure 1b. This ICC is structurally
coordination environment with bond distances rang- similar to the inorganic chain in the 1D compound
3
0
ing from 2.9687(14) to 3.4059(12) Å and bond angles (C H CH NH ) (PbI ) (4). In the packing structure,
10
7
2
3
n
3 n
◦
ranging from 87.36(3) to 177.55(3) . The incomplete the polyanionic chains are located in the rhombic cav-
cubane units, composed of edge-sharing PbI octahe- ities formed by dications to maintain the neutrality of
6
dron centered at Pb1 and Pb2, interlink each other the whole crystal. Solvent DMF molecules are located
through a crystallographic inversion center to form in the voids of the compound. It is electrostatic forces
ICCs extending along a axis, in which neighboring and C–H...I weak interactions between cations and inor-
incomplete cubanes are further consolidated by I2 and ganic chains that pile these components up into a 3D
Figure 2. (a) the structural unit of compound 2; (b) the 1D inorganic chains for compound 2; (c) The
packing diagram of compound 2 view along c axis.
Figure 3. Simulated and experimental PXRD pattern of (a) compound 1, (b) compound 2.

1240
Chengjie Ma et al
stacking structure viewing along a axis, as shown in
figure 1c.
to 3.1032(14) Å. The I-Pb-I bond angles of all bridging
◦
iodo ligands are in the ranges 84.77(4)-94.33(3) and
◦
Compound 2 contains also an incomplete cubane
chain (ICC) acting as the building block of the
inorganic framework and has only subtle differences
in their anionic structure. Compound 2 crystallizes
in the monoclinic space group C2/c. As shown in
figure 2a, Pb center exhibits three coordination modes,
the Pb1 center is six-coordinated in a distorted octa-
1
71.73(3)-178.77(5) , which deviates from the desired
bond angles of octahedra. Two Pb(3) atoms, two Pb(2)
atoms and one Pb(1) atom located in a line. This one-
dimensional chain could be viewed as having two linear
Pb5 fragments which are alternatively stacked by edge-
sharing along the c axis. The structure of compound 2 is
31
similar to the reported compound [(Pb I )(BV) ] and
5
14
2
hedral geometry by four μ -I atoms (I2 and I3) and
2
they both directed by the same dication, the only dif-
ference is Br atom which from the structure-directing
agent coordinates to Pb atom, the coordination environ-
ment of Pb has become more complicated. In packing
structure, the anions moieties and cations counter
cations held together by electrostatic interactions, as
shown in figure 2c view along c axis. The anions located
in the 1D channel stacked by dications along c axis.
two μ -I atoms (I1), the Pb2 center is six-coordinated
3
in a distorted octahedral geometry by three μ -I
2
atoms (I2, I3 and I4), two μ -I atoms (I1) and one
3
μ -Br atom, the Pb3 center is four-coordinated in
2
a distorted tetrahedral geometry by one μ -I atom
2
(
(
I4), two t-Br atoms (Br2 and Br3) and one μ -Br
Br1)atom. The Pb-I distance ranges from 3.1482(11) Å
2
to 3.3365(11) Å, Pb-Br distance ranges from 2.772(2) Å
3.2 Power X-ray Diffraction (PXRD) and
Thermogravimetric Analysis
The experimental PXRD patterns of 1-2 corre-
spond well to the simulated PXRD patterns, indicat-
ing that the bulk phase materials are isomorphous
(
Figure 3).
The TG curves of the two compounds are shown in
figure 4. The TG data indicates that both of the two
◦
compounds were thermally stable up to 250 C. The
decomposition of 1 mainly proceeded in three stages.
◦
The first stage took place in the 45-252 C with 4.09%
loss (calculated ratio 4.38%), which corresponded to
the elimination of solvent DMF molecule; the second
◦
stage in the 357–565 C with 19% loss (calculated ratio
2
5%) mainly involved the removal of dication; The
◦
third stage of compound 1 in the 565-800 C mainly
Figure 4. TG plot of compounds 1 and 2.
involved the extreme burning of inorganic framework.
Figure 5. (a) UV-Vis absorption spectrum of 1 and 2 taken at room temperature; (b) Determination
of the optical band gap of 1 and 2 diffuse reflectance spectrum using the Kubelka-Munk method.

Pb(II) supramolecule directed by conjugated dications
1241
The TG data for 2 shows that the weight loss fast
The title SDAs, 1, 4-PMBP and DBBP, were syn-
from 276 to 387 C with 23% loss (calculated ratio thesised from 4, 4’-bipyridinium with 1, 4-bis (bro-
◦
2
1%), and can be attributed to the loss of dication and momethyl) benzene or benzyl bromide in a certain
some inorganic framework. Then the weight almost ratio and they are both π-conjugated 4, 4’-bipyridine
keeps constant. The second weight loss took place in derivatives dication templates, so the above rule will
◦
the range 516–727 C, which is ascribable to the further not be applicable. Single-crystal X-ray study revealed
burning of mineral phase.
these two PbI compounds both contain incomplete
2
All in all, the thermal behavior of compounds 1 cubane subunit and are similar 1D supramolecules.
and 2 are similar and the loss of organic dications Compared with the reported molecules, most of them
◦
mainly happened near 350–380 C, which means that were synthetized directed by ethyl ammonium alkyl
11,21(b),36
the weak interactions in quantity of CH· · · I/Br have chain derivatives,
π-conjugated dication tem-
limited influence on their thermostability.
plate is rarely reported. Thus, we speculate that PbI2
prefers to form 1D supramolecule which possesses
incomplete cubane subunit directed by π-conjugated
dication templates. The studies described above provide
initial evidence that the formation of supramolecule
3.3 UV-Vis absorption
The solid-state UV-Vis absorption spectra of 1-2 are complex aggregating from the same initial material is
presented in figure 5a. The absorption spectrum exhibits highly dependent on the choice of guest. These novel
peak at 235 nm for 1 (236 nm for 2), which is the supramolecule networks provide not only intriguing
characteristic band of anions assigned as ligand-to- examples of modular chain-framework but also new
metal charge-transfer (LMCT) transition (I→Pb). To insights into the regularity in construction of solid-state
explore the conductivity of compounds 1-2, the UV- materials.
Vis diffuse reflectance spectra of their powder samples
were tested to obtain their band gaps (Eg) by using
the Kubelka-Munk function. As shown in figure 5b.
4
. Conclusion
Their energy gaps (Eg) can be estimated as 2.35 ev for
Two PbI hybrids are obtained via slow evaporation
2
1
and 2.44 ev for 2, respectively. There are tiny blue
at room temperature from methanol and DMF sys-
tem through dication templated self-assembly. As far
as we know, compounds 1 and 2 can be regarded as
shifts of the energy gaps, 0.05 ev for 1 and 0.14 ev
for 2, compared with that of bulk PbI (2.30 eV). The
2
reflectance spectrum measurement revealed the nature
of semiconductor.
1D iodoplumbate examples with incomplete cubane
subunit directed by π-conjugated dication templates.
Hence, similar structured products would be obtained if
we introduce similar templates. More importantly, this
result provides us a new insight into the regularity in
construction of solid-state materials.
3.4 Template effect of title dication
The use of organic species as templating agents has
widened the number and nature of the microporous Acknowledgements
32
crystalline solid phases. The trapped organic moieties
perform several roles: coulombic balance of the neg-
atively charged framework; filling of the microporous
cavities; structuring by the “template effect”. Most sig-
nificantly, the structural information from the organic
template can be imprinted on the final supramolecu-
We gratefully acknowledge the financial support by
the National Natural Science Foundation of China
(
No. 21171148, J1210060) and The Graduate Stu-
dent Self-innovation Project of Zhengzhou University
14LF00620).
(
33
lar frameworks. A template is described as permanent
“internal”) if all the molecular components originally
Supplementary Information
(
34
present are also found in the end product. A recent Crystallographic data reported in this article have been
interesting study showed that in the template effect of deposited with the Cambridge Crystallographic Data
SDA, there exists rigidity/flexibility competition: To Center as supplementary publication. CCDC numbers
some extent, when the spacers are shorter the interac- are 1032768 for 1, 1032769 for 2. These data can be
tion energies are increased; otherwise, the interaction obtained free of charge via http://www.ccdc.cam.ac.uk/
energies decreased. The rigidity/flexibility competition conts/retrieving.html (or from the Cambridge Crystal-
will achieve a balance at a proper point, at which the the lographic Data Center, 12 Union Road, Cambridge CB2
most stable conformation can be presented.35
1EZ, UK; Fax: +44 1223 336 033).

1
242
Chengjie Ma et al
18. (a) Calabrese J, Jones N L, Harlow R L, Herron N,
References
Thorn D L and Wang Y 1991 J. Am. Chem. Soc. 113
2328; (b) Mitzi D B 1996 Chem. Mater. 8 791; (c) Zhu
X H, Mercier N, Riou A, Blanchard P and Frère P 2002
Chem. Commun. 2160; (d) Mercier N 2005 Cryst. Eng.
Comm. 7 429; (e) Billing D G and Lemmerer A 2008
New J. Chem. 32 1736
1
. Yaghi O M, Li H, Davis C, Richardson D and Groy T L
998 Acc. Chem. Res. 31 474
1
2
. (a) Duan H B, Zhao H R, Ren X M, Zhou H, Tian Z F
and Jin W Q 2011 Discuss. Faraday Soc. 40 1672; (b)
Mishra S, Jeanneau E, Daniele S, Ledoux G and Swamy
P N 2008 Inorg. Chem. 47 9333; (c) Chen Y, Yang Z, 19. (a) Corradi A B, Ferrari A M, Pellacani G C, Saccani
Guo C X, Ni C Y, Li H X, Ren Z G and Lang J P
011 CrystEngComm. 13 243; (d) Mishra S, Jeanneau E,
Iasco O, Ledoux G, Luneau D and Daniele S 2012 Eur.
A, Sandrolini F and Sgarabotto P 1999 Inorg. Chem.
38 716; (b) Corradi A B, Ferrari A M, Righi L and
Sgarabotto P 2001 Inorg. Chem. 40 218
2
J. Inorg. Chem. 2012 2749; (e) Krautscheid H, Lode C, 20. Dobrzycki L and Wo z´ niak K 2008 Cryst. Eng. Comm.
Vielsack F and Vollmer H 2001 J. Chem. Soc., Dalton
10 525
Trans. 1099; (f) Tang Z J and Guloy A M 1999 J. Am. 21. (a) Zhang Z J, Xiang S C, Guo G C, Xu G, Wang M S,
Chem. Soc. 121 452
. (a) Yu T L, An L, Zhang L, Shen J J, Fu Y B and Fu Y L
Zou J P, Guo S P and Huang J S 2008 Angew. Chem.
Int. Ed. 47 4149; (b) Krautscheid H, Lekieffre J F and
Besinger J 1996 Z. Anorg. Allg. Chem. 622 1781
3
2014 Cryst. Growth Des. 14 3875; (b) Shen J J, Zhang
C F, Yu T L, An L and Fu Y L 2014 Cryst. Growth Des. 22. Fan L Q, Huang Y Z, Wu L M, Chen L, Li J Q and Ma
E 2006 J. Solid State Chem. 179 2361
14 6337
4
. Blake A J, Champness N R, Hubberstey P, Li W S, 23. Mercier N and Riou A 2004 Chem. Commun. 844
Schrorder M, Withersby M and Schroder M A 1999 24. Billing D G and Lemmerer A 2009 Cryst. Eng. Comm.
Coord. Chem. Rev. 183 117
11 1549
5
. (a) Zheng Z, Yu Z P, Yang M D, Jin F, Ye L N, Fang M, 25. Wang G E, Wang M S, Jiang X M, Liu Z F, Lin R G,
Zhou H P, Wu J Y and Tian Y P 2014 Dalton Trans. 43
139; (b) Jin F, Wang H Z, Zhang Y, Wang Y, Zhang J,
Cai L Z, Guo G C and Huang J S 2011 Inorg. Chem.
Commun. 14 1957
Kong L, Hao F Y, Yang J X, Wu J Y, Tian Y P and Zhou 26. (a) Billing D G and Lemmerer A 2007 Cryst. Eng.
1
H P 2013 Cryst. Eng. Comm. 15 3687
. Sanchez C, Julian B, Belleville P and Popall M 2005 J.
Mater. Chem. 15 3559
Comm. 9 236; (b) Shan Z M, Wang Y L, Guo H X, Liu
Q Y, Zhang N, Yang E L and Li L Q 2011 Inorg. Chim.
Acta. 366 141
6
7
. (a) Wang M S, Xu G, Zhang Z J and Guo G C 2010 27. Geudhr W, Hunig S and Suchy A 1986 Tetrahedron 42
Chem. Commun. 46 361; (b) Pardo R, Zayat M and Levy
D 2011 Chem. Soc. Rev. 40 672
. Wang G E, Jiang X M, Zhang M J, Chen H F, Liu B W,
1665
28. Higashi T and Sagara T 2013 Electrochimica Acta 114
8
105
Wang M S and Guo G C 2013 Cryst. Eng. Comm. 15 29. Sheldrick G M 1997 SHELXTL-97, Program for-
1
0399
. Vincent B R, Robertson K N, Cameron T S and Knop O
987 Can. J. Chem. 65 1024
0. (a) Dobrzycki L and Wo z´ niak K 2008 Cryst. Eng.
Crystal Structure Refinement, University of Gottingen,
Germany
30. Papavassiliou G C, Mousdis G A, Raptopoulou C P and
Terzis A 1999 Z. Naturforsch. B. 54 1405
9
1
1
Comm. 10 577; (b) Dobrzycki L and Wo z´ niak K 2009 J. 31. Chen Y, Wang Z O, Yang Z, Ren Z G, Li H X and Lang
Mol. Struct. 921 18
J P 2010 Dalton Trans. 39 9476
1. Krautscheid H and Vielsack F 1999 J. Chem. Soc. 32. (a) Soler-Illia G J D A A, Sanchez C, Lebeau B,
1
1
1
1
1
1
1
Dalton Trans. 24 2731
Patarin J 2002 Chem. Rev. 102 4093; (b) Huo Q,
Margolese D I, Ciesla U, Demuth D G, Feng P, Gier T E,
Sieger P, Firouzi A and Chmelka B F 1994 Chem. Mater.
6 1176
2. Yue J M, Niu Y Y, Zhang B, Ng S W and Hou H W
2011 Cryst. Eng. Comm. 13 2571
3. Cuna A, Aguiar I, Gancharov A, Pérez M and Fornaro
L 2004 Cryst. Res. Technol. 39 899
33. (a) Alexander K L, Yuen F H, Antony J W, Antony F M
and Thomas M 2012 Microporous Mesoporous Mater.
148 62; (b) Li H H, Chen Z R, Li J Q, Huang C C, Zhang
Y F and Jia G X 2006 Eur. J. Inorg. Chem. 12 2447
34. Hoss R and Vogtle F 1994 Angew. Chem. Int. Ed. 33 375
4. Wang S, Mitzi D B, Feild C A and Guloy A 1995 J. Am.
Chem. Soc. 117 5297
5. Billing D G and Lemmerer A 2006 Cryst. Eng. Comm.
8
686
6. Wang G E, Xu G, Wang M S, Sun J, Xu Z N and Guo 35. Li H H, Xing Y Y, Lian Z X, Gong A W, Wu H Y, Li Y
G C 2012 J. Mater. Chem. 22 16742
and Chen Z R 2013 Cryst. Eng. Comm. 15 1721
7. Wang C H, Ma C J, Huang Z P, Zai Y X, Yang Q, Li L 36. Krautscheid H and Vielsack F 1997 Z. Anorg. Allg.
and Liang Y 2015 J. Clust. Sci. 26 1027
Chem. 623 259