Structural diversity and properties of ZnII and CdII complexes with a flexible dicarboxylate building block 1,3-phenylenediacetate and various heterocyclic co-ligands

Article abstract of DOI:10.1039/b901418g

A series of Zn^II and Cd^II complexes with a flexible dicarboxylate building block and various heterocyclic co-ligands, formulated as {[Zn₂(pda)₂(phen)₂]·2H ₂O}_n (1), {[Zn(pda)(dpe

Full text of DOI:10.1039/b901418g

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Structural diversity and properties of ZnII and CdII complexes with a flexible
dicarboxylate building block 1,3-phenylenediacetate and various heterocyclic
co-ligands†
Mei-Li Zhang,a,b Dong-Sheng Li,*a,b Ji-Jiang Wang,b Feng Fu,b Miao Du,*c Kun Zoua and Xiao-Ming Gaob
Received 23rd January 2009, Accepted 3rd April 2009
First published as an Advance Article on the web 19th May 2009
DOI: 10.1039/b901418g
A series of ZnII and CdII complexes with a flexible dicarboxylate building block and various heterocyclic
co-ligands, formulated as {[Zn2(pda)2(phen)2]·2H2O}n (1), {[Zn(pda)(dpe)]·H2O}n (2), [Zn(pda)(bpp)]n
(3), {[Cd2(pda)2(2,2¢-bipy)2]·2H2O}n (4), {[Cd(pda)(4,4¢-bipy)(H2O)]·H2O}n (5) and {[Cd2(pda)2(bpp)3]·
14H2O}n (6) (pda = 1,3-phenylenediacetate, phen = 1,10-phenanthroline, dpe = 1,2-di(4-pyridyl)-
ethylene, bpp = 1,3-bi(4-pyridyl)propane, 2,2¢-bipy = 2,2¢-bipyridine, and 4,4¢-bipy = 4,4¢-bipyridine),
have been synthesized and structurally characterized. In 1, the (H2O)8 clusters interlink the cyclic
coordination dimers to give a 3D network through hydrogen bonding. Both 2 and 3 feature 2D
corrugated (4,4) layers, which are of 2-fold interpenetrating for 3. In 4, the dimeric CdII subunits are
connected by the 1,3-pda ligands to generate a rampart-shaped 1D chain motif. As for 5, the [Cd(pda)]2
rings are connected by the paired 4,4¢-bipy ligands to afford a tube-shaped 1D motif. In contrast to 1–5,
complex 6 displays a 3D diamond network and, interestingly, the T5(0)A(0)A(2) water tapes are found
to locate in the channels of this 3-D array. A structural comparison of these complexes demonstrates
that the characteristics of auxiliary ligands (from chelating to bridging) play a key role in governing the
coordination motifs as well as the 3-D supramolecular lattices. Solid-state properties such as
photoluminescence and thermal stability of 1–6 have also been studied.
bipy,10 1,2-bis(4-pyridyl)ethane (bpe),11 1,2-di(4-pyridyl)ethylene
(dpe),12 1,3-bi(4-pyridyl)propane (bpp),13 and 1,4-bis(imidazol-1-
Introduction
ylmethyl)benzene (bix)14), and terminal aromatic chelating ligands
(e.g. 2,2¢-bpy,15 1,10-phen,16 and so on), have been widely used for
design and synthesis of functional crystalline solids, especially
coordination polymers.
The prosperous kingdom of crystal engineering has provided
a sound junction between aesthetics of crystalline architec-
tures and their potential functions, of which the ultimate
destination is to successfully obtain the desired materials
with tailored structures and/or physicochemical properties.1
At this stage, the confidence to accomplish this goal is
based upon the sophisticated selection and utilization of
multitopic building blocks as well as tectonic interactions.2,3
So far, some excellent organic tectons, mainly including
the aromatic/heterocyclic multicarboxylate compounds (e.g.
1,4-benzenedicarboxylate,4 1,3,5-benzenetricarboxylate,5 1,2,4,5-
benzenetetracarboxylate,6 pyridine-,7 pyrazole-,8 and imidazole-
dicarboxylate9), neutral organonitrogen bridging ligands (e.g. 4,4¢-
With regard to the aromatic dicarboxylate ligands, the rigid
species such as 1,2-, 1,3-, and 1,4-benzenedicarboxylate (bdc),
have been extensively investigated.17–24 In contrast, the flexible
phenylenediacetic acids (H2pda), also with three possible isomers
of 1,2-, 1,3-, and 1,4-pda, have received less attention. A search of
the Cambridge Structural Database (CSD, July 2008) reveals only
25 reported coordination complexes containing H2pda ligands
(three for 1,2-pda, six for 1,3-pda, and sixteen for 1,4-pda).25 In
comparison with bdc, their two unique structural features inspire
our current research interest. First, owing to the presence of the
flexible –CH2– spacer, the pda ligands can freely bend and rotate
to meet the requirements of the coordination geometries of metal
ions in the assembly process. Second, such ligands may be regarded
as good candidates for constructing novel coordination structures
due to their longer backbones.
On the other hand, polymeric d10 metal (CuI, AgI, AuI, ZnII, or
CdII) complexes have attracted extensive interests in recent years
because they not only exhibit appealing structures but also possess
photoluminescent properties.26 In this regard, to the best of our
knowledge, only fifteen coordination polymers constructed by a
d10 metal and pda ligand have been reported hitherto (three for
1,2-pda, five for 1,3-pda, and seven for 1,4-pda).25a–c,f–j,l,p–r,u In
other words, comprehensive studies of the pda-involved d10 metal
aCollege of Mechanical & Material Engineering, Hubei Key Laboratory of
Natural Products Research and Development, China Three Gorges Univer-
sity, Yichang, 443002, China. E-mail: lidongsheng1@126.com; Fax: +86-
717-6397516; Tel: +86-717-6397516
bCollege of Chemistry and Chemical Engineering, Shaanxi Key Laboratory
of Chemical Reaction Engineering, Yan’an University, Yan’an, 716000,
China
cCollege of Chemistry and Life Science, Tianjin Key Laboratory of Structure
and Performance for Functional Molecule, Tianjin Normal University,
Tianjin, 300387, China. E-mail: dumiao@public.tpt.tj.cn; Fax: +86-22-
23766556; Tel: +86-22-23766556
† Electronic supplementary information (ESI) available: Selected bond
distances and angles, structural diagrams, powder XRD patterns, TGA
curves. CCDC reference numbers 717136–717141 for complexes 1–6. For
ESI and crystallographic data in CIF or other electronic format see DOI:
10.1039/b901418g
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complexes are quite rare, especially in the presence of a secondary
N-donor bridging or chelating co-ligand.
{[Zn(pda)(dpe)]·H2O}n (2). Yield: 30% (based on Zn). Anal.
Calc. for C22H20N2O5Zn: C, 57.72; H, 4.40; N, 6.12. Found: C,
57.32; H, 4.21; N, 6.07%. IR (cm-1): 3435 (br), 2995 (w), 1600 (w),
1550 (s), 1441 (s), 1395 (s), 1292 (m), 1098 (w), 949 (w), 825 (m),
741 (s), 615 (m), 577 (m), 475 (m).
In this contribution, we will describe our recent systematic
research on the preparation, crystal structures, and properties
of a series of ZnII and CdII coordination complexes with 1,3-
pda as well as organonitrogen co-ligands, in which the structural
characteristics of auxiliary ligands vary from chelating to bridging.
On the basis of this result, we aim to further demonstrate
the general coordination chemistry of 1,3-pda, and also the
role of auxiliary ligands on the formation of new coordination
architectures (see Scheme 1).
[Zn(pda)(bpp)]n (3). Yield: 38% (based on Zn). Anal. Calc. for
C46H44N4O8Zn2: C, 60.61; H, 4.86; N, 6.15. Found: C, 60.26; H,
4.54; N, 5.96%. IR (cm-1): 3014 (w), 1625 (s), 1539 (s), 1437 (s),
1359 (s), 1290 (w), 1070 (w), 948 (w), 814 (m), 743 (s), 617 (w), 576
(w), 517 (w).
{[Cd2(pda)2(2,2¢-bipy)2]·2H2O}n (4). Yield: 42% (based on
Cd). Anal. Calc. for C40H36N4O10Cd2: C, 50.17; H, 3.79; N, 5.85.
Found: C, 49.59; H, 3.70; N, 5.70%. IR (cm-1): 3473 (br), 3030 (w),
1585 (s), 1549 (s), 1479 (w), 1435 (w), 1368 (s), 1313 (w), 1159 (m),
1025 (m), 948 (w), 764 (s), 658 (m).
{[Cd(pda)(4,4¢-bipy)(H2O)]·H2O}n (5). Yield: 50% (based on
Cd). Anal. Calc. for C40H40N4O12- Cd2: C, 48.19; H, 4.05; N, 5.62.
Found: C, 48.04; H, 4.00; N, 5.45%. IR (cm-1): 3385 (br), 3037 (w),
1605 (s), 1571 (s), 1489 (m), 1441 (w), 1379 (s), 1309 (w), 1221 (m),
1080 (m), 1010 (m), 810 (s), 721 (s), 667 (w), 631 (s).
{[Cd2(pda)2 (bpp)3]·14H2O}n (6). Yield: 35% (based on Cd).
Anal. Calc. for C59H82N6O20Cd2: C, 49.90; H, 5.82; N, 5.92. Found:
C, 49.50; H, 5.54; N, 5.66%. IR (cm-1): 3420 (br), 2928 (w), 1611
(s), 1575 (s), 1500 (w), 1427 (w), 1396 (s), 1277 (w), 1223 (m), 1070
(w), 1015 (m), 941 (w), 808 (w), 729 (w), 577 (w), 513 (w).
Scheme 1
X-Ray crystallography
Experimental section
Single-crystal X-ray diffraction measurements for complexes 1–6
were carried out on a Bruker APEX II diffractometer equipped
with a graphite crystal monochromator situated in the inci-
dent beam for data collection. The determinations of unit cell
parameters and data collections were performed with Mo Ka
Materials and general methods
All commercially available solvents and reagents for synthesis and
analysis were of reagent grade and used as received. Elemental
analyses of C, H and N were performed on a Perkin-Elmer
2400 CHN elemental analyzer. Infrared spectra on KBr pellets
were recorded on a Bruker Equinox-55 spectrophotometer in
400–4000 cm-1. Thermogravimetric analyses were performed on
a Netzsch STA 449C microanalyzer under air atmosphere at a
heating rate of 10 ◦C min-1. Solid-state fluorescence spectra were
recorded on a Hitachi F-4500 fluorescence spectrophotometer at
room temperature. X-Ray powder diffractions (XRPD) patterns
were recorded on a Shimadzu XRD-7000 X-ray diffractometer
˚
radiation (l = 0.71073 A). Semi-empirical absorption corrections
were applied using SADABS.27 All structures were solved by
direct methods using the SHELXS program of the SHELXTL
package and refined with SHELXL.28 Metal ions were found from
E-maps, and other non-hydrogen atoms were located by successive
difference Fourier syntheses. The final refinement was performed
by full matrix least-squares methods with anisotropic thermal
parameters for non-hydrogen atoms on F2. The hydrogen atoms of
organic ligands were located theoretically and refined with fixed
thermal factors. The water hydrogen atoms were located from
difference maps and refined with isotropic temperature factors.
Notably, the lattice water molecules in complex 6 were refined by
using the pseudo-isotropic “ISOR” restraint as well as the similar
ADP restraint SIMU and the rigid bond restraint DELU to make
the ADP values of the disordered oxygen atoms more reasonable.
Crystallographic data and experimental details for the structural
analyses were summarized in Table 1 and selected bond parameters
were listed in Table S1 (see ESI†).
˚
with Cu Ka radiation (l = 1.5406 A).
Preparation of complexes 1–6
Single-crystal samples of complexes 1–6 were obtained by the same
method as described for 1.
{[Zn2(pda)2(phen)2]·2H2O}n (1). 1 was synthesized hydrother-
mally in a 23 mL teflon-lined autoclave by heating a mixture of
Zn(NO3)2·6H2O (1.0 mmol), H2pda (1.0 mmol), phen (0.5 mmol),
NaOH (2.0 mmol), and H2O (18 mL) at 160 ◦C for 4 days. After
th◦e reactive mixture was cooled to room temperature at a rate of
Results and discussion
5
C h-1 for 2 days, colorless block crystals of 1 were obtained
(yield: 41%, based on Zn). Anal. Calc. for C44H48N4O16Zn2: C,
51.83; H, 4.74; N, 5.49. Found: C, 51.45; H, 4.53; N, 5.31%. IR
(cm-1): 3414 (br), 3059 (w), 1590 (s), 1517 (w), 1423 (m), 1385 (s),
1150 (w), 950 (w), 849 (m), 725 (s), 650 (m).
Synthesis and general characterization
In comparison with bdc, the flexible pda ligands may display
versatile conformations and coordination modes. However, only
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Table 1 Crystal data and structure refinements for complexes 1–6
1
2
3
4
5
6
Empirical formula
Formula weight
Crystal system
Space group
C44H48N4O16Zn2
1019.60
Triclinic
¯
P1
10.483(7)
11.138(7)
12.130(8)
72.197(7)
65.119(7)
68.308(7)
1174.7(1)
1.441
C22H20N2O5Zn
457.77
Triclinic
¯
P1
6.892(1)
9.441(1)
16.151(2)
96.072(2)
101.351(2)
91.589(2)
1023.3(3)
1.486
C46H44N4O8Zn2
911.59
Monoclinic
C40H36N4O10Cd2
957.53
Triclinic
¯
P1
10.902(2)
11.047(2)
15.799(2)
91.546(2)
90.233(2)
94.030(2)
1898.1(7)
1.675
C40H40N4O12Cd2
993.56
Triclinic
¯
P1
7.991(4)
11.514(5)
12.075(5)
107.352(6)
97.505(6)
108.925(6)
970.8(8)
1.699
C59H82N6O20Cd2
1420.11
Monoclinic
C2/c
21.635(2)
13.208(1)
23.307(2)
90
98.206(1)
90
6591.7(1)
1.431
P21/n
˚
a/A
8.534(9)
23.754(3)
10.628(1)
90
98.258(1)
90
2132.2(4)
1.420
2
293(2)
15 952
3973
0.0239
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
3
˚
V/A
Dc/mg m-3
Z
T/K
1
2
2
1
4
293(2)
8383
4239
0.0296
R1 = 0.0407,
wR2 = 0.1047
R1 = 0.0522,
wR2 = 0.1146
528
293(2)
7348
3694
0.0191
R1 = 0.0591,
wR2 = 0.1706
R1 = 0.0655,
wR2 = 0.1761
472
293(2)
14 114
7010
0.0154
R1 = 0.0243,
wR2 = 0.0603
R1 = 0.0286,
wR2 = 0.0631
960
293(2)
5150
3409
0.0172
R1 = 0.0196,
wR2 = 0.0505
R1 = 0.0204,
wR2 = 0.0510
500
293(2)
21 785
6117
0.0239
R1 = 0.0385,
wR2 = 0.1097
R1 = 0.0473,
wR2 = 0.1170
2936
Reflections collected
Reflections unique
Rint
R indices [I > 2s(I)]a
R1 = 0.0271,
wR2 = 0.0644
R1 = 0.0377,
wR2 = 0.0707
944
R indices (all data)b
F(000)
ꢀ
ꢀ
ꢀ
ꢀ
2
a R = ꢀF0| - |FCꢀ/ |F0|. b wR2 = [ [w(F0 - FC2)2]/ [(F02)2]]1/2
.
five coordination complexes with 1,3-pda have been known to
date.25e–i Therefore, in order to systematically study this building
block in the structural assembly of new coordination architectures,
our approach is to introduce different types of N-donor auxiliary
ligands in the systems, which may reduce the available binding sites
of the metal centers.29,30 In addition, the hydrothermal method has
been demonstrated to be a very promising technique for preparing
novel crystalline solids, and thus it was applied in the present work
to successfully synthesize complexes 1–6. The different geometric
needs of the auxiliary ligands will make an important influence on
their final crystal architectures.
Complexes 1–6 are stable at room temperature. Their IR spectra
show the absorption bonds resulting from the skeletal vibrations
of aromatic rings in the 1400–1600 cm-1 range and the broad band
centered at ~3430 cm-1 indicates the O–H stretching of water
(except for 3). The IR spectra also display the characteristic bands
of carboxylate at ~1600/1540 cm-1 for asymmetric vibrations,
and ~1430/1380 cm-1 for symmetric vibrations. Furthermore, the
(nasym - nsym) values are 167/132 cm-1 for 1, 159/155 cm-1 for 2,
188/180 cm-1 for 3, 150/181 cm-1 for 4, 164/192 cm-1 for 5, and
184/179 cm-1 for 6, respectively. The splitting of nasym(–COO)
indicates the different coordination modes of carboxylate,31
being in agreement with their crystal structures. The absence of
characteristic bands at 1730–1690 cm-1 for carboxyl indicates the
complete deprotonation of the ligands in all these complexes.32
square-pyramidal geometry (see Fig. 1a). The 1,3-pda ligand
shows a cis-configuration, in which one carboxylate group adopts
a bidentate chelating mode and the other exhibits a monodentate
coordination mode. Two 1,3-pda ligands link two ZnII ions to form
a cyclic dimer and two terminal chelating phen ligands locate at
both sides of the cycle (Fig. 1a).
In complex 1, the adjacent lattice water molecules are connected
to form a (H2O)8 cluster (see Fig. 1b) via hydrogen bonding33
(see Table S2, ESI†). The water octamer is composed by a water
hexamer adopting the chair conformation and two additional
water pendants at its diagonally opposite ends with a distance
˚
of 2.768(5) A. The average O ◊ ◊ ◊ O distance in the hexamer is
˚
2.734(6) A, which is slightly shorter than those observed in
34,35
˚
liquid water (2.85 A)
ice (Ih, 2.76 A).
and is comparable to that in hexagonal
Moreover, the average O ◊ ◊ ◊ O angle in the
36,37
˚
hexamer is 119.1◦, being larger than the corresponding parameter
in Ih (109.3◦). This 1,4-diaxially substituted chair-like hexameric
conformation for a water octamer is highly unstable with respect
to other fashions of the cluster, as suggested by theoretical
calculations.38
It must be remarked that these water octamers are discrete
and not connected directly to each other. However, six dinuclear
[Zn2(pda)2(phen)2] units are connected to each water cluster
by hydrogen bonds (Fig. S1a, ESI†). Two of the six dinuclear
molecules are linked through the oxygen atoms (O1, O4, O1A, and
O4A) of the carboxylate groups and four water molecules (O5w,
O5wA, O8w, and O8wA) of the hexameric core of the octamer
(O5w–H2w ◊ ◊ ◊ O4 and O8w–H7w ◊ ◊ ◊ O1). The other four dinuclear
molecules are connected to the non-hexameric water molecules of
the octamer (O7w and O7wA). Overall, each dinuclear subunit is
hydrogen bonded to six octamers (Fig. S1b, ESI†). Thus, the water
clusters extend the discrete cyclic dimers to result in a 3D network
through hydrogen bonding (see Fig. 1c).39
Structural description
{[Zn2(pda)2(phen)2]·2H2O}n (1). The asymmetric unit of com-
plex 1 consists of one ZnII ion, one 1,3-pda, one phen, and a
lattice water. Each ZnII ion is surrounded by two nitrogen atoms
from one chelating phen ligand and three oxygen atoms from
two individual m3-1,3-pda anions, composing a slightly distorted
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Fig. 2 (a) Coordination environment around the Zn(II) center in 2 (only
the nitrogen atoms of bpe are shown for clarity). (b) The step-shaped 2D
network of 2.
distorted tetrahedral geometry (see Fig. 3a). The Zn–O and Zn–N
˚
bond distances [1.939(1)–1.967(2) and 2.032(2)–2.038(2) A] and
the bond angles [99.9(6)–115.7(7)◦] in 3 are similar to those in 2.
In 3, the 1,3-pda ligand also shows the trans-configuration
and adopts bis(monodentate) coordination. Along the crystallo-
graphic b axis, the bpp ligands bridge the ZnII centers to form
parallel zigzag chains, which are interconnected to each other
through the 1,3-pda ligands to result in the infinite (4,4) layer
(Fig. 3b). In the layer, two bpp ligands, two 1,3-pda ligands, and
four Zn atoms form a repeating rhombic grid with a side length
˚
of 12.285 ¥ 12.638 A and a diagonal measurement of 18.721 ¥
˚
16.456 A based on the metal–metal distances. Two independent
Fig. 1 (a) Coordination environment around the Zn(II) center in 1.
(b) The structure of one water octamer. (c) Packing diagram of the 2D
array by hydrogen bonding (the phen molecules are omitted for clarity).
(4,4) layers interpenetrate each other in an antiparallel fashion40
(see Fig. 3c and Fig. S2, ESI†). The corrugated nature of the layer
may be attributed to the backbone flexibility of bpp.
When ZnII ion is replaced by CdII, three different complexes 4–6
have been achieved, in which the auxiliary ligands also play an
important role in governing their structures.
When chelating phen is replaced by the bridging bpe and bpp
ligands, respectively, two new 2D complexes 2 and 3 with (4,4)
topology are achieved.
{[Cd2(pda)2(2,2¢-bipy)2]·2H2O}n (4). The structure of complex
4 consists of neutral coordination chains of [Cd2(pda)2(2,2¢-
bipy)2]n and the lattice water molecules. In the chain, there are
two crystallographically independent CdII centers (Cd1 and Cd2),
which adopt different coordination geometries. Cd1 is coordinated
by two nitrogen atoms of one bipy ligand and four oxygen atoms
from three distinct 1,3-pda ligands, while Cd2 is coordinated
by two nitrogen atoms from one bipy ligand and five oxygen
atoms from three 1,3-pda ligands (see Fig. 4a). The bond angles
around Cd1 range from 53.50(6) to 154.19(7)◦, and those around
Cd2 range from 52.60(6) to 149.54(6)◦. The Cd–N [2.330(2)–
{[Zn(pda)(bpe)]·H2O}n (2). As shown in Fig. 2a, the asymmet-
ric unit of 2 comprises one ZnII ion, one 1,3-pda ligand, one bpe
ligand, and a lattice water molecule. Each ZnII ion is surrounded
by two nitrogen atoms from two bridging bpe ligands and two
oxygen atoms from two m2-1,3-pda ligands adopting the trans-
configuration and bis(monodentate) coordination giving a slightly
distorted tetrahedral geometry. The Zn–O and Zn–N bonds
˚
are in the range of 1.945(4)–1.965(4) and 2.053(4)–2.093(2) A,
respectively. In 2, the ZnII centers are connected to each other
by bpe to afford a 1D zigzag chain along the crystallographic b
direction (see Fig. 2b), in which the distance between two adjacent
˚
˚
◦
ZnII ions is 13.411 A and the Zn ◊ ◊ ◊ Zn ◊ ◊ ◊ Zn angle is 102.08 .
2.344(2) A] and Cd–O [2.210(2)–2.628(2) A] lengths are within
the expected range.41
˚
Furthermore, the 1D zigzag chains are interlinked by the 1,3-pda
anions, constituting step-shaped 2D (4,4) networks that stack in a
parallel fashion.
In 4, 1,3-pda shows the trans-configuration and two connecting
modes. The first one adopts the uncommon m5-bridging fashion
to connect three CdII centers, in which the two carboxylate groups
exhibit different metal coordination. The second one adopts the
m4-bridging to connect three CdII ions. Thus, the bimetallic nodes
are linked by two m5-1,3-pda ligands and two m4-1,3-pda ligands
to generate a 1D wavelike double-chain, extending along the
[Zn(pda)(bpp)]n (3). The asymmetric unit of 3 consists of one
ZnII center, one 1,3-pda, and one bpp. Each ZnII ion is surrounded
by two nitrogen donors of two bridging bpp ligands and two
carboxylate oxygen donors of two m2-1,3-pda ligands, affording a
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Fig. 4 (a) Coordination environments around the Cd(II) centers in 4 (only
the nitrogen atoms of bipy are shown for clarity). (b) Rampart-shaped 1D
wavelike motif. (c) Packing diagram of the 1-D arrays through p–p stacking
contacts.
interactions42 between 1,3-pda and 2,2¢-bipy (see Fig. S3b, ESI†).
The centroid-to-centroid and centroid-to-face separations of the
˚
adjacent 2,2¢-bipy an◦d aromatic ring of 1,3-pda are 3.865 A and
˚
3.510 A (angle: 20.84 ), respectively.
{[Cd(pda)(4,4¢-bipy)(H2O)]·H2O}n (5). When the chelating
2,2¢-bipy ligands are replaced by bridging 4,4¢-bipy, a tube-
shaped 1D chain complex 5 with [Cd2pda2] rings is achieved.
The asymmetric unit of 5 comprises of one CdII ion, one 1,3-pda
ligand, one 4,4¢-bipy ligand, one coordination and one lattice
water molecules. Each CdII ion is seven-coordinated to two
nitrogen atoms of two 4,4¢-bipy ligands and five oxygen atoms
of two m4-1,3-pda ligands and one water, fabricating a distorted
penta-bipyramidal geometry (see Fig. 5a). The Cd–N [2.301(2)–
Fig. 3 (a) Coordination environment around the Zn(II) center in 3. (b)
The 2D network structure of complex 3. (c) Perspective view of the two-fold
interpenetrating 2D network of 3.
˚
˚
2.334(2) A] and Cd–O [2.367(2)–2.452(2) A] bond lengths and
the bond angles [53.7(6)–164.9 (6)◦] of 5 are similar to those
of 4.
crystallographic c direction (Fig. 4b). The auxiliary terminal bipy
ligands locate at both sides of the double-chain, leading to the
formation of a rampart-shaped 1D motif. Furthermore, these 1D
arrays are embedded in each other to form a 2D supramolecular
architecture (Fig. 4c and Fig. S3a, ESI†) through p–p stacking
In 5, the 1,3-pda ligand shows the cis-configuration and adopts
bis(bidentate) coordination. It is similar to 1 that two CdII
ions are linked by a pair of 1,3-pda ligands to form a 20-
membered [Cd2pda2] ring. It should be noted that all [Cd2pda2]
rings are connected by two lines of 4,4¢-bipy ligands, forming a
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Fig. 5 (a) Coordination environment around the Cd(II) center in 5 (only
the nitrogen atoms of bipy are shown for clarity). (b) The tube-shaped 1D
chain of complex 5. (c) Packing diagram of the 1-D chains through by
hydrogen bonding.
tube-shaped 1D chain motif (see Fig. 5b). The Cd ◊ ◊ ◊ Cd sepa-
rations across the 1,3-pda and 4,4¢-bipy ligands are 8.189 and
˚
11.694 A, respectively. Furthermore, those 1D arrays are extended
to a 2D supramolecular architecture through hydrogen bonding
Fig. 6 (a) Coordination environment around the Cd(II) center in 6.
(b) The 2D sheet constructed by bridging helical chains through bpp
ligands. (c) Complicated 3D framework of 6 (top) (blue for left-handed
helical chains and red for right-handed helical chains). The diamondoid
framework in 6 (bottom). (d) View of 1D water chain with T5(0)A(0)A(2)
classification. Hydrogen bonding interactions are shown as dashed lines.
[R2 (8)] (see Fig. 5c). In this situation, O2 of carboxylate
2
acts as an H-bond acceptor for the coordinated water molecule
˚
(O5w–H21w ◊ ◊ ◊ O2, 2.705 A) (see Fig. S4, ESI†).
{[Cd2(pda)2(bpp)3]·14H2O}n (6). The asymmetric unit of 6
consists of a CdII ion, one 1,3-pda ligand, one and a half bpp
ligands, as well as seven lattice water molecules. Each CdII center
is seven-coordinated to three nitrogen atoms from three bridging
bpp ligands and four oxygen atoms from two m4-1,3-pda ligands,
forming a distorted penta-bipyramidal geometry (Fig. 6a). The
ESI†). For complexes 3 and 6, the bpp ligands take the TG and
TG/GG¢ conformation, respectively. This difference may mainly
be attributed to the different coordinating surroundings of the
metal cations (four-coordinated for ZnII of complex 3 and seven-
coordinated for CdII of complex 6).
In complex 6, the 1,3-pda ligand shows the cis-configuration
and adopts bis(bidentate) coordination mode. The bpp ligands
adopt different TG and GG¢ conformations, respectively, in which
the GG¢ ones bridge the CdII ions to compose a closed [Cd2bpp2]
ring (Fig. 6c). The 1,3-pda anions bridge the CdII ions to form a
˚
Cd–N [2.359(3)–2.389(3) A] and Cd–O bond distances [2.298(3)–
◦
˚
2.552(3) A] as well as the bond angles [51.9(1)–174.7 (1) ] are
similar to those in 5.
The flexible bpp ligand can adopt different conformations with
respect to relative orientations of the –CH2– groups, such as TT,
TG, GG, and GG¢ (T = trans and G =gauche) (Scheme S1,
5360 | Dalton Trans., 2009, 5355–5364
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1D helical chain around the crystallographic 21 axis, with the pitch
it can still be regarded that the bulk as-synthesized materials
represent complexes 1–6.
˚
of 13.208 A (see Fig. 6b). Moreover, these helical chains are united
together through the TG bpp ligands to afford a 2D helical layer
(Fig. 6b). A careful examination shows that the helices in layer
A are exclusively right-handed, whereas those in the neighboring
layer B are left-handed (see Fig. 6c). Namely, the helices in adjacent
layers A and B are pairs of enantiomers, which are pillared by the
GG¢ bpp ligands to form a 3D mesomeric framework (see Fig. 6c).
In this net, the CdII ions and ligands act as 4- and 2-connected
nodes, respectively, resulting in a 4-connected diamond topology
(see Fig. 6c).
Another interesting structural feature of 6 is that, coursing the
3D open framework along [001], the crystallizing water molecules
are interconnected by hydrogen bonding to form the water tapes
based on (H2O)14 cluster (see Fig. 6d), in which the (H2O)14
subunit involves two same cyclic water pentamers (O1w–O5w
and O1wA–O5wA) and a two-molecular water chain (O7w and
O7wA) outfitted with two pendent water molecules (O6w and
O6wA) on two sides. The H-bonding parameters are summarized
in Table S2 (ESI†). Within the water tape, the cyclic water
pentamers are almost coplanar with the average hydrogen-bonded
Thermal stability of complexes 1–6 has been investigated by
thermogravimetric analysis (TGA) technique and the TGA curves
are shown in Fig. S7 (ESI†). For 2, the weight loss between 25
◦
and 120 C corresponds to the release of water molecules (obsd:
3.6% and calcd: 3.9%). The removal of organic components occurs
at 440 ◦C. For 3, there are no lattice and coordination water
molecules and thus decomposition of the organic components
occurs at 430 ◦C. For 4, the weight loss attributed to the gradual
release of water molecules is observed in the range 25–160 ◦C
(obsd: 3.6% and calcd: 3.8%). The decomposition of residual
composition occurs at 250 ◦C. For 5, it loses the lattice and
coordination water molecules from 25 to 200 ◦C (obsd: 7.0%
and calcd: 7.2%). The anhydrous composition is stable up to
290 ◦C. As for 1, the weight loss corresponding to the release
of water molecules is observed from 25 to 120 ◦C (obsd: 3.4%
and calcd: 3.5%), leaving a framework of [Zn2(pda)2(phen)2]. This
framework remains stable to 310 ◦C, upon which it begins to
decompose. The PXRD patterns for complex 1 at 200 and 300 ◦C
are the same (Fig. S6, ESI†), indicating that the host structure is
maintained. For 6, the◦TGA curve shows two consecutive steps of
weight loss in 25–200 C, corresponding to evacuation of lattice
water molecules (obsd: 18.1% and calcd: 17.8%). The anhydrous
composition begins to decompose at 270 ◦C, and this is also
confirmed by the PXRD patterns (see Fig. S6, beyond 270 ◦C, the
diffraction peaks of CdO appear). Notably, temperature-variable
PXRD patterns of 6 (see Fig. S6) also reveal that the lattice
structure is stable up to at least 270 ◦C, in which all water moieties
are excluded. For 1–6, the remaining weight indicates that the final
residue is ZnO or CdO.
˚
distance of 2.717 A, which is comparable to the average hydrogen-
43
˚
bonded distance of the cyclic water pentamer (2.716 A). And a
wide variation in the hydrogen-bonded O ◊ ◊ ◊ O distances (2.370–
◦
˚
3.058 A), O ◊ ◊ ◊ O ◊ ◊ ◊ O angles (77.4–167.4 ), and O–H ◊ ◊ ◊ O angles
(111–171◦) provides flexibility to the water molecules in this
environment so that they can be accommodated in the channels
with the aid of hydrogen bonding to the oxygen atoms of 1,3-pda
(Fig. S5, ESI†), and at the same time can maximize the interactions
among themselves. Just by strong interpentamer O5w ◊ ◊ ◊ O5wB
hydrogen bonds, the (H2O)14 clusters are assembled to an extended
tape with a T5(0)A(0)A(2) motif44 (Fig. 6d). To our knowledge,
such an arrangement of water tapes has not been reported so far.45
In complexes 1–6, the 1,3-pda ligand displays diversiform
bridging fashions in the structural assembly. This is reasonable
as 1,3-pda is a flexible dicarboxylate ligand, and it can take
versatile coordination modes. Thus, the complexes containing
1,3-pda generally show 2D or 3D structures. In this work, when
the auxiliary terminal ligands phen and 2,2¢-bipy are introduced,
the expected 0D cyclic dimeric complex 1 and rampart-shaped
1D wavelike chain complex 2 are obtained. On the other hand,
when the auxiliary bridging ligands 4,4¢-bipy, bpe, and bpp are
introduced into the systems, the resulting complexes 2, 3, 5, and
6 show step-shaped 2D network, interpenetrating 2D double-
layer structure, tube-shaped 1D chain motif, and 3D helical open
framework, respectively. These results suggest that the structural
characteristics of auxiliary ligands play an important role in
governing the structures of such supramolecular complexes.
Luminescent properties
Solid-state luminescent emission spectra of complexes 1–6 are
depicted in Fig. 7. The intense broad photoluminescence emissions
are found at 399 nm (lex = 330 nm) for 1, at 415 nm (lex
=
300 nm) for 2, at 352 nm (lex = 300 nm) for 3, at 393 nm
(lex = 322 nm) for 4, at 366 nm (lex = 300 nm) for 5, and
at 377 nm (lex = 330 nm) for 6. In order to understand the
nature of the emission band, the photoluminescence property of
free H2pda ligand was measured with the observation of one
weak emission at 367 nm (lex = 300 nm). In comparison to
the free ligand, most of the emission maxima of complexes 1–6
are changed, which are neither metal-to-ligand charge transfer
PXRD and TGA results
In order to confirm the phase purity of the bulk materials,
powder X-ray diffraction (PXRD) experiments were carried out
for complexes 1–6. The PXRD patterns at different temperatures
for complexes 1 and 6, at room temperature for complexes 2–5 are
shown in Fig. S6 (ESI†). Although the experimental patterns have
a few unindexed diffraction peaks and some are slightly broadened
in comparison to those simulated from the single-crystal data,
Fig. 7 Solid-state emission spectra of 1–6 at room temperature.
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(MLCT) nor ligand-to-metal transfer (LMCT) in nature, since
the ZnII and CdII ions are difficult to oxidize or reduce. Thus,
they may be assigned to intraligand (p–p*) fluorescent emission.46
Many aromatic ligands that are not strongly emissive themselves
display significant luminescence when coordinated to ZnII or
CdII.47 The enhancement of luminescence is perhaps a result of
the coordination effect of those ligands to the metal center, which
effectively increases the rigidity of ligands, thereby reducing the
non-radiative decay of the intraligand (p–p*) excited state.48
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Conclusions
A series of ZnII and CdII coordination supramolecular com-
plexes with a flexible dicarboxylate ligand have been synthesized
and structurally characterized, and the present work provides
a systematic exploration on the design and construction of
diverse polymeric networks by changing the auxiliary ligands. The
resultant coordination frameworks, varying from 0D (1), 1D (4
and 5), 2D (2 and 3), to 3D (6), are profoundly influenced by the
auxiliary ligands as well as metal ions. We are currently preparing
other metal complexes with 1,2-, 1,3- and 1,4-pda modules and
different N-donor ligands.
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Acknowledgements
7 (a) L.-L. Wen, D.-B. Dang, C.-Y. Duan, Y.-Z. Li, Z.-F. Tian and Q.-J.
Meng, Inorg. Chem., 2005, 44, 7161; (b) H.-L. Gao, L. Yi, B. Zhao,
X.-Q. Zhao, P. Cheng, D.-Z. Liao and S.-P. Yan, Inorg. Chem., 2006,
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Wang, W. Shi, Y. Ma, H.-B. Song, P. Cheng, D.-Z. Liao and S.-P. Yan,
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This work was supported by the National Natural Science
Foundation of China (20773104), the Program for New Century
Excellent Talents in University (NCET-06-0891), the Natural
Science Foundation of Hubei Provinces of China (2008CDB030),
the Key Project of Key Laboratory of Shaanxi Province (08JZ81),
and the Important Project of Hubei Provincial Education Office
(2009HB33 Z20091301). M.D. also thanks the support from
Tianjin Normal University.
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