Self-assembly of two fluorescent supramolecular frameworks constructed from unsymmetrical benzene tricarboxylate and bipyridine

Article abstract of DOI:10.1016/j.ica.2007.01.023

Two new supramolecular compounds, [Ag(4,4′-bipy)]_n [Ag(HBTC)]_n (1) and [Cu(H₂BTC)(2,2′-bipy)] (2) (HBTC/H₂BTC = 1,2,4-benzenetricarboxylate, 4,4′-bipy/2,2′-bipy = 4,4′/2,2′-bipyridine), have been synthesized and characterized by elemental analyses, IR spectra, ultraviolet-visible diffuse reflection integral spectra (UV-Vis DRIS), fluorescent spectra, thermogravimetric analysis and single crystal X-ray diffraction analysis. It is noteworthy that there were two kinds of one-dimensional stairs-chain including cationic [Ag(4,4′-bipy)]_n chain and anionic [Ag(HBTC)]_n chain in 1. Furthermore, a two-dimensional double layer supramolecular framework was constructed through coordination bonds, hydrogen bonds, π-π stacking interactions and Ag?O weak coordinative interactions. The one-dimensional supramolecular chain of 2 was built from combining mononuclear [Cu(H₂BTC)(2,2′-bipy)] by inter- and intra-molecular hydrogen bonding interactions. Additionally, the two complexes exhibit intense blue or olivine luminescence at room temperature.

Full text of DOI:10.1016/j.ica.2007.01.023

Inorganica Chimica Acta 360 (2007) 2704–2710
www.elsevier.com/locate/ica
Self-assembly of two fluorescent supramolecular frameworks
constructed from unsymmetrical benzene tricarboxylate and bipyridine
*
Shuai Zhang, Zhen Wang, Hanhui Zhang , Yanning Cao, Yanxiang Sun, Yiping Chen,
Changcang Huang, Xiaohong Yu
Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002, PR China
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou,
Fujian 350002, PR China
Received 27 November 2006; received in revised form 26 January 2007; accepted 26 January 2007
Available online 4 February 2007
Abstract
Two new supramolecular compounds, [Ag(4,40-bipy)]n [Ag(HBTC)]n (1) and [Cu(H2BTC)(2,20-bipy)] (2) (HBTC/H2BTC = 1,2,4-ben-
zenetricarboxylate, 4,40-bipy/2,20-bipy = 4,40/2,20-bipyridine), have been synthesized and characterized by elemental analyses, IR spec-
tra, ultraviolet–visible diffuse reflection integral spectra (UV–Vis DRIS), fluorescent spectra, thermogravimetric analysis and single
crystal X-ray diffraction analysis. It is noteworthy that there were two kinds of one-dimensional stairs-chain including cationic
[Ag(4,40-bipy)]n chain and anionic [Ag(HBTC)]n chain in 1. Furthermore, a two-dimensional double layer supramolecular framework
was constructed through coordination bonds, hydrogen bonds, p–p stacking interactions and Agꢀ ꢀ ꢀO weak coordinative interactions.
The one-dimensional supramolecular chain of 2 was built from combining mononuclear [Cu(H2BTC)(2,20-bipy)] by inter- and intra-
molecular hydrogen bonding interactions. Additionally, the two complexes exhibit intense blue or olivine luminescence at room
temperature.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Silver; Copper(I); Mixed ligands; Hydrogen bonds; Supramolecular framework
1. Introduction
tional intermolecular interaction that may control short-
range packing [9], and many investigations have paid atten-
tion to hydrogen bond [10–13]. As polycarboxylate acids can
act as hydrogen bond accepter as well as donor [14], it is go
without saying that polycarboxylate acids are able to con-
struct the supramolecular architectures. Recently, a great
achievement has been obtained in the field of polycarboxy-
late metal–organic polymers for their intriguing structural
features, physical and chemical properties [15,16]. The versa-
tile polycarboxylate ligands can build different dimension
compounds according to the symmetry of acids. In general,
symmetric benzene polycarboxylate acids, such as 1,4-ben-
zenedicarboxylic acid [17–19], 1,3,5-benzenetricarboxylic
acid [20–25] and 1,2,4,5-benzenetetracarboxylic acid [26–
29], are prone to build high dimensional porous framework
with applications in exchange of guest molecules [30]. Con-
trastly, asymmetric rigid benzene polycarboxylate acids,
The contemporary interest in supramolecular chemistry is
due to the novel structural topologies and potential applica-
tions in host–guest chemistry, catalysis, photochemistry, and
electrical conductivity [1–3]. In the past decades, the develop-
ment of supramolecular assembled chemistry has made it
possible to rationally design and synthesize supramolecular
architectures through supramolecular interactions (hydro-
gen bonding, p–p stacking interaction and weak coordina-
tive interaction, etc.) [4–8]. There is no doubt that the
hydrogen bond is the most familiar organizing force in
supramolecular assembly owing to its moderately direc-
*
Corresponding author. Address: Department of Chemistry, Fuzhou
University, Fuzhou, Fujian 350002, PR China. Fax: +86 591 87893239.
E-mail address: zhanghh1840@hotmail.com (H. Zhang).
0020-1693/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2007.01.023

S. Zhang et al. / Inorganica Chimica Acta 360 (2007) 2704–2710
2705
such as 1,2,4-benzenetricarboxylic acid (H3BTC) is easier to
2.2. Synthesis of compounds
form low dimensional compounds [31–33]. However, it does
not mean that the research on asymmetric benzene polycarb-
oxylate acids is meaningless. By virtue of high asymmetry
and rich coordinate modes [34], it can result in high asym-
metric molecules or supramolecules, structural varieties
and form novel frameworks by special orientations of the
carboxylate groups [35], which cannot be achieved by other
symmetric benzene polycarboxylate acids [36]. Additionally,
introduction of other N-containing bidentate organic
ligands to H3BTC system, such as bipyridine acting as both
chelating and linear ligand, will not only certain provide
more complicated and interesting compounds, but might
endow final products with intriguing and applicable proper-
ties. However, due to the different solubility and coordina-
tion competition of the ligands, syntheses of compounds
containing mixed ligands are more difficult to control than
those containing only one. Hydrothermal synthesis has been
proved to be an effective and promising method to minimize
the differential solubility problems [37].To our best knowl-
edge, there are only a few reported compounds based on
mixed BTC with other ligands [38–48]. So, our research
group has put our eyes on synthesizing the novel supramo-
lecular compounds with unsymmetrical benzene carboxy-
lates and bipyridine under hydrothermal conditions. In
this article, the hydrothermal reactions of the carboxylate-
based ligand TMA (TMA = 1,2,4-benzenetricarboxylic
anhydride), which hydrolyzed to HBTC or H2BTC, with
metal salts and bipyridine as a second linker, afforded two
new supramolecular compounds, namely [Ag(4,40-bipy)]n
[Ag(HBTC)]n Æ 1 with a novel 2-D double layer supramolec-
ular framework formed by two kinds of weakly connected
silver-containing molecular ladder and [Cu(H2BTC)(2,20-
bipy)] (2) with 1-D infinite supramolecular chain structure
formed by hydrogen bonding interactions. Herein, we report
their syntheses, crystal structures and spectroscopic
properties.
Synthesis of 1: AgNO3 (0.085 g, 0.50 mmol) and TMA
(0.096 g, 0.50 mmol) were dissolved in 6 mL of distilled
water by vigorous stirring. 4,40-bipy (0.064 g, 0.40 mmol)
was added to the mixture and stirred for 10 min. The
resulting solution was sealed in a Teflon-lined stainless
autoclave and heated at 130 °C for 3 days under autoge-
nous pressure and then cooled to room temperature during
6 h. Colorless block crystals of 1 suitable for X-ray analysis
were harvested in 63% yield (based on silver). Anal. Calc.
for C19H12O6N2Ag2: C, 39.34; H, 2.09; N, 4.83. Found:
C, 38.66; H, 2.29; N, 4.94%. IR (KBr, cmꢁ1): 3406 (vs),
3047 (m), 1691 (s), 1579 (vs), 1564 (vs), 1493 (vs), 1412
(s), 1363 (s), 1174 (m), 1140 (m), 1101(m), 806 (vs), 760
(s), 702 (m).
Synthesis of 2: A mixture of CuI (0.190 g, 1 mmol), KI
(0.332 g, 2 mmol), TMA (0.096 g, 0.50 mmol) and 2,20-bipy
(0.064 g, 0.40 mmol) in 6 mL distilled water was sealed in a
Teflon-lined stainless autoclave and heated at 120 °C for 3
days under autogenous pressure and then cooled to room
temperature during 6 h. Red parallelepiped crystals of 2
suitable for X-ray analysis were obtained in about 90%
yield (based on 2,20-bipy). Anal. Calc. for C19H13O6-
N2Cu: C, 53.21; H, 3.06; N, 6.53. Found: C, 53.04; H,
3.68; N, 6.92%. IR (KBr, cmꢁ1): 3518 (vs), 3070 (m),
1709 (s), 1658 (vs), 1577 (vs), 1471 (s), 1376 (s), 842 (vs),
766 (s), 694 (m).
2.3. X-ray crystallography
The reflection intensities for 1 and 2 were collected on a
Rigaku Weissenburg IP diffractometer with Mo Ka radia-
˚
tion (k = 0.71073 A) at 298 2 K. Lp correction and a w
empirical absorption correction were made for the intensity
data. The structures of 1 and 2 were solved by the direct
methods and successive Fourier difference syntheses, and
refined by the full-matrix least-squares method on F2 with
anisotropic thermal parameters for all non-hydrogen
atoms. The remaining hydrogen atoms were generated geo-
metrically and not refined. In compound 1, the Ag(2) atom
is disorder and possesses two positions with occupancies
given in parentheses: Ag(2A) (87.5%), Ag(2B) (12.5%).
Further details of the crystallographic data and structure
refinement for both are summarized in Table 1. Selected
bond lengths and angels are given in Table 2. All calcula-
tions were performed on a computer with SHELXTL-PC pro-
gram package [49,50].
2. Experimental
2.1. General procedures
All analytical regent grade chemicals were commercially
purchased and used without purification. The elemental
analyses of C, H, and N were performed with an Elementar
Vario EL III elemental analyzer. The IR spectra were
recorded with a Perkin–Elmer Spectrum 2000 FT-IR spec-
trometer in the range of 400–4000 cmꢁ1 using the KBr pel-
let technique. The UV–Vis DRIS spectrum was measured
by a Perkin–Elmer Lambda 900 UV–Vis spectrometer.
Thermogravimetric (TG) analyses were conducted on a
Perkin–Elmer TGA7 Thermal Analyzer in an argon atmo-
sphere with a heating rate of 10 °C/min from room temper-
ature to 800 °C. The fluorescent spectra were recorded on
an Edinburgh Instrument FL/FS-920 fluorescent spec-
trometer using Xe lamp for steady fluorescent and H2
nanosecond flash lamp for transient fluorescence.
3. Results and discussion
3.1. Structure description of 1
X-ray diffraction analysis shows 1 contains two weakly
connected silver-containing chains which alternate with each
other, namely cationic [Ag(4,40-bipy)]n chain and anionic
[Ag(HBTC)]n chain, and a 2-D supramolecular framework

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S. Zhang et al. / Inorganica Chimica Acta 360 (2007) 2704–2710
0
˚
Table 1
and Ag(1)–N(2) = 2.147(3) A], generating the [Ag(4,4 -
bipy)]n chain, two of which are linked into a 1-D molecular
ladder by weak coordinative Agꢀ ꢀ ꢀO interaction [Ag(1)–
Crystallographic data and structure refinement for 1 and 2
Compound
1
2
˚
˚
O(2) = 2.695(2) A and Ag(1)–O(2C) = 2.706(8) A] (Fig. 1).
Empirical Formula
Formula mass
Crystal system
Space group
C19H12O6N2Ag2 C19H13O6N2Cu
580.05
triclinic
P1
8.055(5)
9.869(5)
11.322(7)
76.52(2)
79.83(3)
77.73(2)
847.6(8)
2.273
2
564
0.71073
3.00–27.47
8425
3857 (0.0172)
3323
R1a = 0.0340,
wR2b = 0.0927
R1 = 0.0397,
wR2 = 0.0954
˚
428.85
triclinic
P1
The distance of Ag(1)ꢀ ꢀ ꢀAg(1) is 3.727 A, which is signifi-
cantly longer than the van der Waals contact whose distance
ꢀ
ꢀ
˚
is 3.40 A, illustrating the lack of direct metal–metal contact
between Ag(1) ions. Additionally, the distance between the
centroids of the pyridyl rings (3.89 A) exceeds the maximum
contact for the p–p stacking interaction (3.8 A for centroid–
centroid distance), indicating no obvious p–p stacking inter-
action [53,54]. Ag(2) is in a tetrahedral position coordinated
by four oxygen atoms from three different HBTC anions.
The [Ag(HBTC)]n linear chain generates from two HBTC
units both in the chelating and monodentate form. [Ag(2)–
˚
a (A)
8.150(6)
9.004(5)
12.369(7)
96.46(2)
95.47(3)
110.88(3)
833.7(9)
1.708
2
436
0.71073
3.18–27.48
8266
3791 (0.0230)
3287
R1a = 0.0699,
wR2b = 0.2232
R1 = 0.0755,
wR2 = 0.2279
˚
b (A)
˚
˚
c (A)
˚
a (°)
b (°)
c (°)
3
˚
V (A )
Dcalc (g/cm3)
Z
F(000)
k(Mo Ka) (A)
h Range (°)
Collected reflections
Independent reflections (Rint
Observed reflections (I > 2r(I))
Final R factors (I > 2r(I))
˚
˚
˚
O(3) = 2.208(3) A, Ag(2)–O(5) = 2.348(3) A and Ag(2)–
O(6) = 2.613(2) A]. Furthermore, every two chains are also
linked into a 1-D molecular ladder by weak coordinative
˚
)
˚
Agꢀ ꢀ ꢀO interaction [Ag(2)–O(4) = 2.663(2) A] and strong
intermolecular hydrogen bonding interactions between 2-
carboxyl oxygen O(1) of one HBTC and the other one oxy-
gen O(6) of the 4-carboxyl of another opposite HBTC
Final R factors (all data)
˚
[O(1)–O(6) = 2.520(4) A] (Fig. 2). The hydrogen bond is
illustrated in Table 3 in detail. In addition, the parallel ben-
zene rings of HBTC anions are separated by 3.67 A (cen-
troid–centroid), showing the existence of weak p–p
Largest difference map in peak and 0.93 and ꢁ1.07 1.97 and ꢁ0.78
ꢁ3
˚
hole (e A
)
P
P
˚
a
R1 ¼ jjF oj ꢁ jF cjj= jF oj.
P
P
2
2
1=2
b
wR2 ¼ f ½wðF 2o ꢁ F cÞ ꢂ= ½wðF 2oÞ ꢂg
.
stacking interaction which strengthens the forming of 1-D
˚
ladder either. The distance of Ag(2)ꢀ ꢀ ꢀAg(2) is 3.471 A, indi-
constructed through coordination bonds, hydrogen bonds,
p–p stacking interaction and Agꢀ ꢀ ꢀO weak coordinative
interactions. To the best of our knowledge, the example con-
sisting of independently cationic and anionic chains in a
supramolecular framework in silver–carboxylate complexes
is rare [51], which is also unwonted in other metal–organic
complexes [52]. Apparently, we can see that during this
hydrothermal synthesis TMA hydrolyzed to HBTC which
also happened in the progress of synthesizing compound 2.
As shown in Fig. 1, two crystallographically independent sil-
ver(I) atoms are present: Ag(1) and Ag(2). Ag(1) atom is
cating the absence of direct metal–metal contact between
Ag(2) ions either. From the whole aspect, a 2-D double layer
structure of 1 was constructed (Fig. 2).
3.2. Structural description of 2
The immediate coordination environment around the
Cu centers in compound 2 is shown in Fig. 3. The
Cu(I) centers lie in a trigonal planner environment. Struc-
tural evidence has been reported for some three-coordi-
nate copper(I) complexes with trigonal planner
geometry, which usually happens in the copper(I) halides
[55–57]. Bond distances around the Cu centers, N(1)–
0
˚
bonded to two 4,4 -bipy units [Ag(1)–N(1) = 2.143(3) A
˚
˚
Cu(1), 2.274(6) A, N(2)–Cu(1), 2.348(6) A and with
O(1)–Cu(1), 2.219(5) A, are slight longer than previously
Table 2
˚
˚
Selected bond lengths (A) and angles (°) for 1 and 2
Complex 1[c]
reported copper(I) complexes [56–58] containing carboxy-
lates and nitrogen donor ligands. The deprotonated tricar-
boxylic acid function forms a six-member ring in which
the hydrogen was located between two oxygens of 1-
and 2-carboxyl within one H2BTC, O(3) and O(2). And
Ag(1)–N(1)#1
Ag(1)–O(2)
O(5)–Ag(2)#2
2.143(3)
2.695(2)
2.348(3)
Ag(1)-N(2)
Ag(1)–O(2)#3
Ag(2)–O(3)
2.147(3)
2.706(8)
2.208(3)
Ag(2)–O(5)#1
N(1)#1–Ag(1)–N(2)
C(16)–O(5)–Ag(2)#2
2.348(3)
173.84(13)
98.8(2)
O(3)–Ag(2)–O(5)#1
C(11)–O(3)–Ag(2)
149.20(12)
110.5(3)
˚
they are separated by 2.404(7) A, indicative of a much
stronger intra-molecular hydrogen bonding interaction.
The distance of O(4) from the 1-carboxyl of one
H2BTC and O(16) from the 4-carboxyl of the adjacent
Complex 2
Cu(1)–O(1)
Cu(1)–N(2)
2.219(5)
2.348(6)
Cu(1)–N(1)
2.274(6)
˚
H2BTC molecule (2.635(6) A) clearly illustrates strong
intermolecular hydrogen bonding between the monomeric
units, which further form a 1-D supramolecular chain
structure (Fig. 4). The details of hydrogen bonds are sum-
marized in Table 3 as well.
O(1)–Cu(1)–N(1)
N(1)–Cu(1)–N(2)
[c]
150.7(2)
72.0(2)
O(1)–Cu(1)–N(2)
C(11)–O(1)–Cu(1)
135.01(19)
108.2(4)
Symmetry codes: #1 1 + x, ꢁ1 + y, z; #2 ꢁ1 + x, 1 + y, z, #3 1 ꢁ x,
1 ꢁ y, ꢁz.

S. Zhang et al. / Inorganica Chimica Acta 360 (2007) 2704–2710
2707
Fig. 1. Perspective view of the coordination environment of the Ag(I) ion in 1. Hydrogen atoms were removed for clarity. Symmetry code for the
generated atoms: A (1 ꢁ x, ꢁy, 1 ꢁ z); B (1 + x,ꢁ1 + y, z); C (1 ꢁ x, 1 ꢁ y, ꢁz).
Fig. 2. 2-D double-layer structure of complex 1 formed by weakly connected two kinds of molecular ladders. The hydrogen bonding interactions are
represented by thick black dashed lines. The thin black dashed lines between HBTC molecules stand for the p–p stacking interaction. Hydrogen atoms
were removed for clarity.
3.3. Spectroscopy
at 1493–1579 cmꢁ1 and 1363–1412 cmꢁ1 for 1, 1577–1658
and 1376–1471 cmꢁ1 for 2 are attributed to asymmetric
and symmetrical stretching vibrations of the coordinated
carboxylate groups respectively. According to Kazou
Nakamoto [59], we can infer the coordination modes of
The IR spectra of 1 and 2 show the presence of par-
tially deprotonated tricarboxyl groups fairly by virtue of
the absorption around 1700 cmꢁ1. The strong absorptions
Table 3
˚
Hydrogen bonds lengths (A) and angles (°) for 1 and 2
Compound
D–H
d(D–H)
d(Hꢀ ꢀ ꢀA)
1.71
1.68
1.83
\DHA
d(Dꢀ ꢀ ꢀA)
2.520(4)
2.404(7)
2.635(6)
A
1
2
O1–H20
O3–H13
O16–H6
0.82
0.82
0.82
168.1
146.8
166.9
O6[d]
O2
O4[e]
[d]
[e]
Symmetry codes: [ꢁx, ꢁy + 1, ꢁz + 1]; [x + 1, y + 1, z].

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S. Zhang et al. / Inorganica Chimica Acta 360 (2007) 2704–2710
The UV–Vis DRIS spectra of both similarly display two
intense absorptions at 239 and 297 nm, 244 and 299 nm
respectively (Fig. 5), indicating that electronic transitions
are mostly p–p* and n–p* originating from the phenyl
and pyridyl groups [17].
Fig. 6 shows the emission spectra of the complex 1 and 2
in the solid state at room temperature. Upon photoexcita-
tion, complex 1 exhibits an intense fluorescent emission
band with a maximum at 502 nm (kex = 410 nm), while 2
shows two fluorescence signals at 475 and 534 nm
(kex = 390 nm). What’s more, complex 1 and 2 shows anal-
ogous but obviously weaker fluorescence signals at 444 nm
(kex = 360 nm).These emissions may be assigned to the
metal-to-ligand-charge-transfer bands (MLCT) [56]. Addi-
tionally, it is noticeable that the complex 1 and 2 exhibit a
quenching of the fluorescence with lifetime s = 6.40 and
13.62 ns. These observations suggest that 1 and 2 may be
used as advanced materials for blue-light or olivine-light
emitting diode device.
Fig. 3. Perspective view of the coordination environment of the Cu(I) ion
in 2. Hydrogen atoms of aromatic ring were omitted for clarity.
carboxyl groups. In compound 1, the D(D = mas ꢁ ms) cov-
ers a wide range which shows various coordinate modes
of the carboxyl groups in HBTC. This is accordance with
the result of X-ray diffraction analysis which also indi-
cates the bridging unidentate, bridging bidentate and che-
lating bidentate modes of the carboxyl groups of the
HBTC ligand coordinating to Ag(I) centers. In contrast,
for compound 2, the value of D is above 200 cmꢁ1, which
illustrates the unidentate coordinate mode of the carboxyl
groups and the X-ray diffraction is identical with this
inference as well.
3.4. Thermal analysis
To characterize the thermal stability of supramolecular
frameworks constructed from unsymmetrical benzene tri-
carboxylate and bipyridine, the complexes 1 and 2 were
investigated by the TG techniques. There is only one step
Fig. 4. 1-D chain structure formed by hydrogen bonding interactions, which are represented by black dashed lines. Hydrogen atoms were removed for
clarity.
Fig. 5. UV–Vis DRIS spectra of 1 (left) and 2 (right).

S. Zhang et al. / Inorganica Chimica Acta 360 (2007) 2704–2710
2709
Fig. 6. Solid-state emission spectra of 1 (left) and 2 (right) at room temperature.
mass loss in the TG curve of 1, which is stable until 249 °C.
Appendix A. Supplementary material
The weight loss of 61.2% (calc. 63.21%) observed from 250
to 360 °C corresponds to the release of HBTC and 4,40-bipy
which indicates that these two ligands are lost in the same
time and Ag2O (38.8%) is the last product after decomposi-
tion. As for 2, weight loss occurs in the range of 240–
662 °C, corresponding to the lost of the release of H2BTC
and 2,20-bipy, and the total weight loss is 83.3% (calc.
85.18%).
CCDC 296079 and 296080 contain the supplementary
crystallographic data for 1 and 2. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.ica.2007.01.023.
4. Conclusions
In summary, two novel supramolecular compounds 1
and 2 were successfully synthesized under hydrothermal
conditions, in which TMA hydrolyzed to HBTC/H2BTC.
It proves the capability of hydrothermal reactions in pre-
paring novel supramolecular materials with mixed organic
ligands. The structure of compound 1 is intriguing owing to
the alternate independent cationic and anionic chains
which were connected by weak Agꢀ ꢀ ꢀO interactions. In
addition, it is noteworthy that hydrogen bonds play impor-
tant role in building supramolecular architecture which can
be reflected from the synthesizing of 2. Furthermore, both
the complexes possess an intense fluorescence property at
room temperature, which exhibiting potential application
in acting as light emitting diode device. Further study of
synthesizing supramolecular compounds based on TMA
and N-heteroaromatic ligands under hydrothermal condi-
tion is underway to probe into the role of hydrogen bonds
in supramolecular chemistry and their applications.
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This work was supported by the Young Talent Pro-
grammed of Fujian Province (Project No. 2006F3072),
the State Key Laboratory of Structural Chemistry, Fujian
Institute of Research on the Structure of Matter, Chinese
Academy of Sciences and Fuzhou University Young Talent
Programmed.
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