Noncentrosymmetric organic solid and its zinc coordination polymer with diamonded network prepared from an ionothermal reaction: Syntheses, crystal structures, and second-order nonlinear optics properties

Article abstract of DOI:10.1021/cg300889x

An organic ligand 4-(1,2,4-triazol-1-yl) benzoic acid (Htzbc) with a nonlinear optical (NLO) chromophore has been synthesized. Reaction of Zn(NO ₃)₂ with Htzbc ligand in 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid af

Full text of DOI:10.1021/cg300889x

Article
pubs.acs.org/crystal
Noncentrosymmetric Organic Solid and Its Zinc Coordination
Polymer with Diamonded Network Prepared from an Ionothermal
Reaction: Syntheses, Crystal Structures, and Second-Order Nonlinear
Optics Properties
†
†
†
‡
‡
,†,‡
Yu-Ling Wang, Jiang-Hong Fu, Jia-Jia Wei, Xiang Xu, Xin-Fa Li, and Qing-Yan Liu*
†
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. China
‡
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 350002, P. R. China
*
S Supporting Information
ABSTRACT: An organic ligand 4-(1,2,4-triazol-1-yl) benzoic
acid (Htzbc) with a nonlinear optical (NLO) chromophore has
been synthesized. Reaction of Zn(NO ) with Htzbc ligand in 1-
3
2
n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid
afforded compound Zn(tzbc) (1). The Htzbc organic solid
2
and 1 crystallize in the acentric Pn and Cc space groups,
2
+
respectively. The tetrahedral Zn center in 1 coordinates to two
triazole nitrogen atoms and two carboxylate oxygen atoms from
four tzbc− ligands, leading to a noncentrosymmetric 5-fold
interpenetrating diamondoid network. Second-harmonic gen-
eration (SHG) measurements revealed the Htzbc solid and 1
have SHG activities. The Htzbc compound has a large SHG
effect, which is approximately 3 times that of KDP and is type-I
phase matchable, while 1 also belongs to phase-matchable class with a SHG response of about 1.2 times that of KDP. The SHG
active of the organic solid can be derived from the inherently dipolar Htzbc molecule as well as the optimal relative orientation of
the molecular NLO-phores in the crystal packing. The odd number-fold interpenetrated diamondoid network with dipolar NLO
chromophoric units based on asymmetrical bridging ligands and metal centers results in the SHG activity of 1. In addition,
elemental analysis, IR spectra, powder X-ray diffraction patterns (PXRD), and thermogravimetric analysis of both compounds are
described.
INTRODUCTION
carefully choosing an organic molecule with appropriate β value
and controlling the reaction conditions, the centrosymmetric
alignment of molecular dipoles can be avoided, which leads to
■
The synthesis of new materials possessing crystallographic
noncentrosymmetry (NCS) has attracted the interest of both
the physicist and chemist communities because of their
symmetry-dependent properties such as piezoelectricity,
ferroelectricity, pyroelectricity, and second-order nonlinear
4
second harmonic generation (SHG) active materials. Herein a
new 4-(1,2,4-triazol-1-yl) benzoic acid compound with a five-
membered triazole group and benzoic acid moiety has been
synthesized. It shows a SHG response resulting from the
inherent NLO chromophore of the organic molecules and the
asymmetric arrangement of the dipolar molecules in the crystal
lattice.
1
optics (NLO). In the past few decades, much effort has so
far been concentrated on the inorganic oxide crystals based on
0
the octahedral coordinated d transition-metal ions such as
4
+
5+
6+
6+
4+
4+
Ti ,V , Mo , and W and lone-pair-containing Te , Se ,
and I5+ cations because both of them are susceptible to second-
On the other hand, metal−organic coordination compounds
2
or metal−organic frameworks (MOFs) have currently emerged
order Jahn−Teller (SOJT) distortions. The NCS organic
5
as a new type of potential NLO material. Using a combination
molecules with large first hyperpolarizability β are also highly
3
of the well-defined geometry of the metal centers and organic
sought after. Most of the organic molecules with large β values
ligands containing appropriate functional groups, NCS
having a good electron donor and acceptor moieties are
electronically asymmetric and highly dipolar. However, in their
solid states the chromophores tend to pack antiparallel because
of the strong dipole−dipole interactions, which induces the
formation of centrosymmetric molecular arrangements and
leads to centrosymmetric crystals. Therefore, the construction
of an organic NLO material remains a significant challenge. By
6
coordination compounds can be obtained. By employing the
rigid conjugated bridging ligand with unsymmetrical linking
Received: July 2, 2012
Revised: August 15, 2012
Published: August 16, 2012
©
2012 American Chemical Society
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Article
groups that introduce the electronic asymmetric, Lin has
successfully demonstrated a useful approach to construction of
mol) and potassium carbonate (4.6 g 0.033 mol) in 50 mL three-neck
flask under stirring. The reaction mixture was heated at 90 °C for 5
min. Then 4-fluorobenzaldehyde (2.302 g 0.033 mol) was gradually
added to a stirred solution of the reaction mixture. The resulting
mixture was vigorously stirred at 90 °C for 24 h to form a yellow
precipitate. After cooling of the mixture to room temperature, 50 mL
of ice water was added to the reaction mixture. The resulting yellow
10
NCS d -metal-based coordination polymers with diamonded
7
networks. Reaction of the zinc salt with the asymmetrical 4-
(1,2,4-triazol-1-yl) benzoic acid (Htzbc) ligand with NLO
chromophore under ionothermal conditions yielded a NCS
coordination polymer of 1. Compound 1 displaying an odd
number-fold interpenetrated diamonded network shows a
second-order NLO effect. It should be noted that the
ionothermal condition effectively prevents the coordination of
solvent molecules from tetrahedral zinc centers, thus forming
the NCS structure. Herein we present the syntheses, crystal
structures, and SHG properties of the Htzbc compound and
the zinc compound.
precipitate was collected by filtration and washed with Et O (5 mL).
2
The product was dried at 60 °C to afford the intermediate 4-(1,2,4-
triazol-1-yl) benzaldehyde. 4-(1,2,4-Triazol-1-yl) benzaldehyde (1.74 g
0.01 mol) and AgNO (3.4 g 0.02 mol) were added to a 60 mL 70%
3
NaOH solution in 150 mL flask. The reaction mixture was slowly
heated to 60 °C and stirred for 24 h at this temperature. After cooling
to room temperature, the insoluble material was removed by filtration
and then rinsed with H O (20 mL). The filtrate was acidified (pH ≈
2
2
) by addition of concentrated HCl to form a yellow precipitate. The
yellow precipitate was collected by filtration and washed with Et O (5
2
EXPERIMENTAL SECTION
General. All chemicals were reagent grade and used as
commercially obtained from Sinopharm Chemical Reagent Co., Ltd.,
China.
NMR Spectrum, Elemental Analysis, and Infrared Spectros-
copy. NMR analyses were recorded on a Bruker Avance 400
spectrometer equipped with an automatic sample holder. Chemical
shift data for each signal are reported in ppm units with DMSO as
reference, where δ (DMSO) = 2.50 ppm. Elemental analyses were
carried out on an Elementar Vario EL III analyzer, and IR spectra (KBr
pellets) were recorded on PerkinElmer Spectrum One.
mL). The crude product was recrystallized from hot DMF to yield the
■
1
Htzbc solid as colorless crystals. Yield 1.22 g (65%). H NMR (400
MHz, DMSO-d , δ, ppm): 13.10 (s, 1H), 9.41(s, 1H), 8.29 (s, 1H),
6
8
.12 (d, 2H), and 8.02 (d, 2H). Anal. Calcd. for C H N O (189.18):
9 7 3 2
C, 57.14; H, 3.73; N, 22.21%. Found: C, 57.01; H, 3.76; N, 22.14%. IR
−1
spectrum (cm , KBr pellet): 3444 (m), 3131 (m), 1692 (s), 1641
(w), 1606 (s), 1558 (m), 1525 (m), 1446 (s), 1385 (w), 1346 (w),
1317 (m), 1272 (s), 1224 (m), 1138 (s), 1123 (s), 1067 (s), 973 (w),
953 (m), 823 (w), 801 (w), 772 (m), 692 (w), 671 (m), 644 (w), 619
(w), 562 (w), 538 (w), 516 (w).
Synthesis of Zn(tzbc) (1). Zn(NO ) ·6H O (0.0595 g, 0.2
2 3 2 2
Second-Order NLO Measurements. The measurement of the
mmol) and 4-(1,2,4-triazol-1-yl)benzoic acid (0.0756 g, 0.4 mmol)
were mixed with 0.6 g of 1-n-butyl-3-methylimidazolium tetrafluor-
oborate in a 15 mL Parr Teflon-lined stainless steel vessel. The vessel
was sealed and heated to 160 °C. This temperature was kept for 6 days
and then the mixture was cooled naturally to form colorless crystals of
1 (yield: 0.054 g, 62% on the basis of Zn). Anal. Calcd. for
powder frequency-doubling effect was carried out by means of the
8
method of Kurtz and Perry. The fundamental wavelength is 1064 nm
generated by a Q-switched Nd:YAG laser with a frequency doubling at
32 nm. SHG efficiency has been shown to depend strongly on
particle size; thus samples of Htzbc and compound 1 were ground and
sieved into several distinct particle size ranges (45−53, 53−75, 74−
05, 105−150, 150−210 μm). The samples were pressed into a disk
with a diameter of 8 mm that was put between glass microscope slides
and secured with tape in a 1-mm thick aluminum holder, and a
powdered KDP sample used as the reference was sieved into the same
size range. No index-matching fluid was used in any of the
experiments.
5
C H N O Zn (441.71): C, 48.95; H, 2.74; N, 19.03%. Found: C,
18 12 6 4
−1
1
48.91; H, 2.68; N, 19.01%. Main IR features (cm , KBr pellet): 3443
(w), 3131 (w), 1687 (s), 1608 (s), 1568 (m), 1542 (m), 1504 (m),
1492 (m), 1462 (w), 1427 (w), 1384 (s), 1297 (s), 1219 (m), 1142
(s), 1045 (s), 1068 (m), 1002 (w), 975 (m), 955 (m), 860 (m), 809
(w), 771 (m), 690 (w), 670 (m), 638 (w), 559 (w), 538 (w), 516 (w).
X-ray Crystallography. Single crystal X-ray diffraction data of
Htzbc compound and compound 1 were collected on a Bruker Apex II
CCD diffractometer equipped with a graphite-monochromated Mo−
Kα radiation (λ = 0.71073 Å). Data reduction was performed using
SAINT and corrected for Lorentz and polarization effects. Adsorption
Thermogravimetric Analysis. The thermogravimetric measure-
ments were performed with a Netzsch STA449C apparatus under a
nitrogen atmosphere with a heating rate of 10 °C/min in the Al O
2
3
containers. Temperature intervals are 30−400 °C for organic
1
0
compound and 30−600 °C for compound 1, respectively.
corrections were applied using the SADABS routine. The structures
Powder X-ray Diffraction. Powder X-ray diffraction patterns were
performed on a Rigaku Miniflex Π powder diffractmeter using Cu−Kα
radiation (λ = 1.5418 Å) at room temperature. The 2θ range was 5−
were solved by the direct methods and successive Fourier difference
2
syntheses, and refined by the full-matrix least-squares method on F
1
1
(SHELXTL, version 5.1). All non-hydrogen atoms are refined with
6
0° with a continuous scan step width of 0.05°. The recorded patterns
anisotropic thermal parameters. Hydrogen atoms were assigned to
were compared with theoretical patterns calculated from single-crystal
calculated positions. The R
1
values are defined as R
1
= Σ||F
o
| − |F
) ]} . The details of the
o
c
||/ Σ|
2
2
2
2
2
1/2
structure data (Figure S2 in the Supporting Information).
F
o
| and wR
2
= {Σ[w(F
o
− F
c
) ]/Σ[w(F
Synthesis of Htzbc Ligand (Scheme 1). The Htzbc ligand was
crystal parameters, data collection, and refinement are summarized in
9
prepared following a modified known procedure. 0.1 mL of
Table 1.
tricaprylylmethylammonium chloride was added dropwise to a 10
mL of DMF containing a mixture of 1H-1,2,4-triazole (2.302 g 0.033
RESULTS AND DISCUSSION
■
Syntheses. Ionothermal synthesis, the use of an ionic liquid
as solvent in the preparation of crystalline solids, is a new
synthetic methodology developed recently. Compared with the
traditional hydro(solvo)thermal methods, the change from
molecular to ionic reaction media leads to new types of
materials with structural properties that are much different than
those obtained using a routine synthetic approach. Reaction of
Zn(NO ) with Htzbc ligand in 1-n-butyl-3-methylimidazolium
Scheme 1. Preparation of Htzbc Ligand
3
2
tetrafluoroborate solvent afforded compound 1. However,
replacing the 1-n-butyl-3-methylimidazolium tetrafluoroborate
solvent with aqueous solvent in a similar reaction leads to a
12
mononuclear structure of Zn(tzbc) (H O) , where the zinc
2
2
4
4
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Crystal Growth & Design
Article
Table 1. Crystallographic Data for Htzbc Ligand and
Compound 1
Compound 1 is crystallized in the noncentrosymmetric space
group Cc, as a result of the unsymmetrical nature of organic
ligand. There is one zinc(II) ion and two tzbc monoanions in
a
−
Htzbc
1
the asymmetric unit. As depicted in Figure 3, the Zn1 ion
coordinates to two nitrogen atoms and two carboxylate oxygen
formula
fw
C H N O
C H N O Zn
9
7
3
2
18 12
6
4
189.18
296(2)
441.71
−
atoms of four tzbc ligands in a distorted tetrahedral geometry,
temp (K)
cryst syst
space group
Z
296(2)
which is different from the octahedral coordination geometry of
monoclinic
Pn
monoclinic
the zinc center in compound Zn(tzbc) (H O) obtained under
2
2
4
Cc
12
hydrothermal reaction. The Zn−O bond distances are
2
4
1
.908(2) and 1.9418(19) Å, and the Zn−N bond distances
a (Å)
3.96260(10)
6.2888(2)
16.5205(5)
90
12.4567(16)
20.188(3)
8.1381(10)
90
are 2.015(2) and 2.023(2) Å, respectively. The Zn(II) centers
b (Å)
−
are bridged by the tzbc ligands in a bidentate bridging fashion
c (Å)
through the monodentate carboxylate and triazole groups, to
give a 3D framework featuring a diamondoid network (Figure
α (deg)
β (deg)
94.462(2)
90
115.5500(10)
90
4
). With Zn···Zn separations of 12.24 and 12.31 Å, a large void
γ (deg)
V (Å3)
Dcalcd (g·cm−3)
is generated within a single diamondoid cage. For such an
empty framework (Figure 4), structural interpenetration is
difficult to avoid. Actually, the void space in 1 is filled by the
formation of a 5-fold diamondoid structure, in which five
independent diamond nets are mutually interpenetrated in a
parallel mode (Figure 5). We have thus demonstrated that
acentric polymeric networks based on diamondoid structures
can be readily constructed with a judicious choice of
unsymmetrical bridging ligands.
410.44(2)
1.531
1846.4(4)
1.589
−
1
μ (mm
)
0.113
1.370
no. of reflns collected
independent reflns
obsd reflns (I > 2σ(I))
F(000)
3628
8434
1428
4116
1230
3750
196
896
Flack parameter
R[int]
−0.3(15)
0.0194
0.0331
0.0832
0.009(10)
0.0239
0.0291
0.0716
R1 (I > 2σ(I))
IR Spectra, Thermal Analyses and Powder X-ray
Diffraction Patterns. The characteristic band at 1692 cm−
in the IR spectrum of compound Htzbc is attributable to the
carboxylic acid group. The IR spectrum of compound Htzbc
1
wR (all data)
2
a
2
2 2
R1 = Σ||F | − |F ||/Σ|F | and wR = {Σ[w(Fo − Fc ) ]/
o
c
o
2
2
2
1/2
Σ[w(Fo ) ]}
.
−1
shows the typical asymmetric (1606 cm ) and symmetric
−1
(
1446 cm ) stretching bands of carboxylate group. The strong
center is six-coordinated by four aqua ligands and two nitrogen
−1
−1
bands at 1687 and 1608 cm , and 1384 cm , respectively,
correspond to the asymmetric and symmetric stretching bands
of the carboxylate groups in the IR spectrum of compound 1.
Powder X-ray diffraction (PXRD) has been used to check the
phase purity of the bulky samples in the solid state. For
compounds Htzbc and 1, the measured PXRD patterns very
closely match the simulated patterns generated from the results
of single-crystal diffraction data (Figure S2 in the Supporting
Information), indicative of pure products.
−
atoms of two tzbc monoanions. Thus the noncentrosymmetric
3D structure of 1 is much different from the centrosymmetric
mononuclear structure of Zn(tzbc) (H O) synthesized under
2
2
4
hydrothermal conditions. The result clearly shows that the
ionothermal reaction can effectively prevent the coordination of
solvent molecules such as H O and DMF to the zinc center.
2
Crystal Structures. Single-crystal X-ray diffraction analyses
revealed that the Htzbc solid crystallizes in the noncentrosym-
metric monoclinic space group Pn with one molecule in the
asymmetric unit. The O−H···N hydrogen bonds between the
carboxylic hydrogen and triazole nitrogen atom with an O···N
distance of 2.697(3) Å link the Htzbc molecules to form a 1D
infinite chain as shown in Figure 1. The 1D chains are stacked
parallelly to give a 2D layer spreading out the ac plane. The
interchain π−π interactions with a center-to-center distance of
To study the stability of compounds Htzbc and 1,
thermogravimetric analysis (TGA) studies were performed.
The results of the thermal analyses are represented by the
curves in Figure S3, Supporting Information. The Htzbc
organic compound is stable up to 185 °C and then exhibits two
main steps of weight losses. The first step (185−210 °C)
corresponds to the release of the carboxyl group (weight loss:
measured 22.79%, theoretical 23.81%). The combustion of the
aromatic portion of the organic ligand occurs at 225 °C and
ends at 320 °C. The TGA trace for compound 1 displays a
continual weight loss occurring at 330 °C. Before 330 °C there
3
.96 Å between the parallel aromatic rings are observed (Figure
S1 in the Supporting Information). 2D layers are packed along
the (010) axis to give a 3D crystal packing in which the
interlayer C−H···O (C···O = 3.26 Å) interactions are observed
(
Figure 2).
Figure 1. The Htzbc molecules are linked by hydrogen bonds to give a 1D chain.
4
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Crystal Growth & Design
Article
Figure 2. 3D crystal packing of the Htzbc solid. Dotted lines indicate the hydrogen bonds.
Figure 3. An adamantanoid cage in 1 showing the coordination
environment of the Zn(II) center.
Figure 5. A schematic view of the 5-fold interpenetrated diamondoid
networks in 1.
measurements on the sieved powder samples revealed that both
compounds display SHG signals. The SHG intensities for
Htzbc and compound 1 are about 3 and 1.2 times that of KDP
in the particle size of 150−210 μm (Figure 6), which confirms
their acentricity as well as to evaluate their potential as second-
order NLO materials. The plots of the SHG signals as a
function of particle size ranging from 45 to 210 μm measured
on ground crystals suggest both compounds are type-I phase-
matchable (Figure 6), which is a necessary character for a NLO
material to serve for laser frequency converting. The SHG
intensity of 1 (1.2 × KDP and 19 × α-quartz) is similar to that
of 5-fold interpenetrating diamondoid network Cd(pyb) ·H O
Figure 4. A single 3D diamondoid framework in 1.
2
2
(
18 × α-quartz) (pyb = 4-(pyridin-4-yl)benzoate) constructed
13
is a small gradual mass loss, which can be ascribed to the
instability of the electronic balance.
from the analogous ligands. However, their SHG intensities
are lower than those of Zn(4-pya) (pya = (E)-3-(pyridin-3-
2
1
4
Second-Harmonic Generation (SHG) Properties. Since
Htzbc organic solid and compound 1 crystallize in non-
centrosymmetric space groups, it is worthy to study their SHG
properties. The SHG properties have been measured using the
Kurtz−Perry powder SHG technique with a Q-switch Nd:YAG
laser of wavelength 1064 nm and KDP as a reference. SHG
yl)acrylate),1 Zn(imac) ·H O (imac = (E)-3-(imidazol-4-
2
2
5
yl)acrylate), and (Me NH )[CdLi(odba) ] (odba = 4,4′-
2
2
2
oxidibenzoate) with 5-fold interpenetrating diamondoid net-
16
works.
As is well-known, the second-order NLO effect from
molecular crystals is sensitive to the molecular hyperpolariz-
4
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Crystal Growth & Design
Article
Figure 6. Oscilloscope traces of the SHG signals of KDP, Htzbc, and Zn(tzbc) at the same particle size of 150−210 μm (left) and SHG
2
measurements of ground Htzbc and Zn(tzbc) crystals with KDP as the reference (right).
2
ability as well as the relative disposition of the molecules in the
crystal lattice. The total macroscopic dipolar moment must not
be equal to zero, which is essential for a second-order NLO
material. As depicted in Figure 1, the Htzbc molecules adopt a
head-to-tail alignment in the 1D hydrogen-bonded zigzag chain
and the neighboring chains are stacked parallelly along the ac
plane (Figure S1 in Supporting Information). Moreover, the
ASSOCIATED CONTENT
Supporting Information
X-ray structure data in CIF format; 2D hydrogen-bonded
structure for Htzbc compound; powder X-ray diffraction
patterns; TG curves. This material is available free of charge
via the Internet at http://pubs.acs.org.
■
*
S
AUTHOR INFORMATION
Corresponding Author
E-mail: qyliuchem@hotmail.com. Fax: +86-791-88120380.
2
2
D layers are further stacked parallelly along the b axis (Figure
). It is clear that the magnitudes of dipole moments along the
■
*
b axis are canceled and the vector sum of them is well enhanced
along the ac plane, which leads to the large SHG response of
the Htzbc solid. For 1, the odd-fold interpenetrated diamond-
oid networks in a parallel mode with dipolar NLO
chromophoric units based on asymmetrical bridging ligands
and metal centers contribute the SHG activity of 1. However,
the SHG response of 1 is less intense than that of the organic
solid. In 1 the Htzbc ligand is coordinated to the zinc centers.
The dihedral angles between the benzoate group and triazole
group of the two independent Htzbc ligands in 1 are 29.6 and
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the NNSF of China (Grants
0901033 and 21101081), the Scientific Research Foundation
for the Returned Overseas Chinese Scholars (State Education
Ministry), the Provincial NSF of Jiangxi (2009GZH0056), and
the Project of Education Department of Jiangxi Province
GJJ10016 and GJJ11381). The authors thank Professor Jiang-
Gao Mao for helpful assistance in measuring the SHG
properties.
■
2
(
39.7°, while in Htzbc solid the dihedral angle between the
benzoate group and triazole group is 13.9°, which indicates that
the effect of conjugation of the organic ligand is larger in the
organic solid than that in compound 1. That is to say, the
molecular hyperpolarizability β of the organic ligand in the
organic solid is larger than that in compound 1. In a
microscopic view, the second-order NLO susceptibility is
related to the molecular hyperpolarizability β of a molecule. As
these results the SHG intensity of 1 is lower than that of the
Htzbc organic solid.
REFERENCES
■
2
(1) (a) Ok, K. M.; Chi, E. O.; Halasyamani, P. S. Chem. Soc. Rev.
006, 35, 710. (b) Evans, O.; Lin, W. Acc. Chem. Res. 2002, 35, 511.
c) Zhang, W.; Xiong, R. -G. Chem. Rev. 2012, 112, 1163. (d) Bella, S.
D. Chem. Soc. Rev. 2001, 30, 355. (e) Hang, T.; Zhang, W.; Ye, H. -Y.;
Xiong, R.-G. Chem. Soc. Rev. 2011, 40, 3577.
2) (a) Chang, H.-Y.; Kim, S.-H.; Halasyamani, P. S.; Ok, K. M. J.
Am. Chem. Soc. 2009, 131, 2426. (b) Sun, C.-F.; Hu, C.-L.; Xu, X.;
Ling, J.-B.; Hu, T.; Kong, F.; Long, X.-F.; Mao, J.-G. J. Am. Chem. Soc.
(
(
2
009, 131, 9486. (c) Phanon, D.; Gautier-Luneau, I. Angew. Chem., Int.
CONCLUSIONS
■
Ed. 2007, 46, 8488. (d) Hubbard, D. J.; Johnston, A. R.; Casalongue,
H. S.; Sarjeant, A. N.; Norquist, A. J. Inorg. Chem. 2008, 47, 8518.
In conclusion, an organic solid of 4-(1,2,4-triazol-1-yl) benzoic
acid (Htzbc) with nonlinear optical (NLO) chromophore and
its zinc compound with 5-fold interpenetrating diamondoid
network prepared under ionothermal condition have been
reported. Both compounds crystallize in the acentric space
groups. SHG measurements revealed that both compounds are
SHG activities and show type-I phase matchable behavior. This
demonstrates that ionothermal synthesis can provide a simple
and effective approach to the discovery of new nonlinear optics
crystalline material.
(
e) Wang, L.; Pan, S.; Chang, L.; Hu, J.; Yu, H. Inorg. Chem. 2012, 51,
852.
3) (a) Prakash, M. J.; Radhakrishnan, T. P. Chem. Mater. 2006, 18,
943. (b) Fu, D. -W.; Zhang, W.; Cai, H.-L.; Zhang, Y; Ge, J.-Z.;
Xiong, R.-G.; Huang, S. D. J. Am. Chem. Soc. 2011, 133, 12780.
c) Liao, Y.; Eichinger, B. E.; Firestone, K. A.; Haller, M.; Luo, J.;
1
(
2
(
Kaminsky, W.; Benedict, J. B.; Reid, P. J.; Jen, A. K.-Y.; Dalton, L. R.;
Robinson, B. H. J. Am. Chem. Soc. 2005, 127, 2758.
(
Des. 2008, 8, 2589. (b) Horiuchi, S.; Tokura, Y. Nat. Mater. 2008, 7,
357. (c) Zhao, H.; Li, Y.-H.; Wang, X.-S.; Qu, Z.-R.; Wang, L.-Z.;
4) (a) Wampler, R. D.; Begue, N. J.; Simpson, G. J. Cryst. Growth
4
667
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Crystal Growth & Design
Article
Xiong, R.-G.; Abrahams, B. F.; Xue, Z. Chem.Eur. J. 2004, 10, 2386.
(
d) Cai, H.-L.; Zhang, W.; Ge, J.-Z.; Zhang, Y.; Awaga, K.; Nakamura,
T.; Xiong, R.-G. Phys. Rev. Lett. 2011, 107, 147601.
5) (a) Liu, Y.; Li, G.; Li, X.; Cui, Y. Angew. Chem., Int. Ed. 2007, 46,
301. (b) Ye, H.-Y.; Fu, D. W.; Zhang, W.; Zhang, Y.; Xiong, R.-G.;
(
6
Huang, S. D. J. Am. Chem. Soc. 2009, 131, 42. (c) Sun, H.-L.; Ma, B.-
Q.; Gao, S.; Batten, S. R. Cryst. Growth Des. 2006, 6, 1261. (d) Zhao,
H.; Qu, Z.-R.; Ye, H.-Y.; Xiong, R.-G. Chem. Soc. Rev. 2008, 37, 84.
(
e) Fu, D.-W.; Zhang, W.; Cai, H.-L.; Zhang, Y.; Ge, J.-Z.; Xiong, R.-
G.; Huang, S. D.; Nakamura, T. Angew. Chem., Int. Ed. 2011, 50,
1947.
6) (a) Liu, Q.-Y.; Wang, Y. L.; Shan, Z.-M.; Cao, R.; Jiang, Y.-L.;
1
(
Wang, Z.-J.; Yang, E.-L. Inorg. Chem. 2010, 49, 8191. (b) Li, L. N.; Ma,
J. X.; Song, C.; Chen, T. L.; Sun, Z. H.; Wang, S. Y.; Luo, J. H.; Hong,
M. C. Inorg. Chem. 2012, 51, 2438. (c) Xiong, R.-G.; Xue, X.; Zhao,
H.; You, X.-Z.; Abrahams, B. F.; Xue, Z. Angew. Chem., Int. Ed. 2002,
41, 3800.
(
(
(
7) Wang, C.; Zhang, T.; Lin, W. Chem. Rev. 2012, 112, 1084.
8) Kurtz, S. W.; Perry, T. T. J. Appl. Phys. 1968, 39, 3798.
9) (a) Jin, F.; Ma, J.; Ma, J.-L.; Cui, Y. M.; Wu, J. Y.; Tian, Y.-P.
Chem. J. Chin. Univ. 2006, 27, 1599. (b) Geng, W.-Q.; Zhou, H.-P.;
Cheng, L.-H.; Hao, F.-Y.; Xu, G.-Y.; Zhou, F.-X.; Yu, Z.-P.; Zheng, Z.;
Wang, J.-Q.; Wu, J.-Y.; Tian, Y.-P. Polyhedron 2012, 31, 738.
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10) Sheldrick, G. M. SADABS; University of Gottingen, 1995.
11) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112.
12) Unpublished result. Crystal data for compound
Zn(tzbc) (H O) (C H N O Zn): M = 513.79, triclinic, space
2
2
4
18 20
6
8
r
group P1
̅
, a = 6.1760(7) Å, b = 6.9979(8) Å, c = 12.1225(14) Å, α =
o
o
o
3
80.6540(10) , β = 87.9520(10) , γ = 72.0230(10) , V = 491.67(10) Å ,
3
−1
Z = 1, Dcalc = 1.735 mg/m , μ = 1.313 mm , F(000) = 264, R =
1
0
.0245, wR = 0.0640.
2
(
13) Evans, O. R.; Xiong, R. G.; Wang, Z. Y.; Wong, G. K.; Lin, W.
Angew. Chem., Int. Ed. 1999, 38, 536.
(
14) Evans, O. R.; Lin, W. Chem. Mater. 2001, 13, 2705.
(
15) Feng, X.; Wen, Y. H.; Lan, Y. Z.; Feng, Y. L.; Pan, C. Y.; Yao, Y.
G. Inorg. Chem. Commun. 2009, 12, 89.
16) Lin, J. D.; Long, X. F.; Lin, P.; Du, S. W. Cryst. Growth Des.
010, 10, 146.
(
2
4
668
dx.doi.org/10.1021/cg300889x | Cryst. Growth Des. 2012, 12, 4663−4668