Two chiral nonlinear optical coordination networks based on interwoven two-dimensional square grids of double helices

Article abstract of DOI:10.1021/cg101135r

Two new chiral two-dimensional coordination networks, ZnL ₂(H₂O)₂ (1) and CdL₂(H ₂O)₂ (2) [L = 1,2,2-trimethyl-3-(pyridin-4-ylcarbamoyl) cyclopentanecarboxylic acid], have been synthesized and structurally characterized by single X-ray structure analysis, featuring very unusual interwoven (4,4) square grids of double helices. The frameworks exhibit high thermal stability as confirmed by thermogravimetric analysis and powder X-ray diffraction studies. The unique chiral networks attributed to the chiral organic linker have led to their nonlinear optical properties.

Full text of DOI:10.1021/cg101135r

DOI: 10.1021/cg101135r
Two Chiral Nonlinear Optical Coordination Networks Based on
Interwoven Two-Dimensional Square Grids of Double Helices
2010, Vol. 10
5291–5296
Qian Huang,† Jiancan Yu,† Junkuo Gao,† Xingtang Rao,† Xiuli Yang,§ Yuanjing Cui,†
Chuande Wu,§ Zhangjing Zhang,‡ Shengchang Xiang,‡ Banglin Chen,*,‡ and
Guodong Qian*,†
†State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering,
Zhejiang University, Hangzhou 310027, China, ‡Department of Chemistry, University of Texas at
San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, United States, and §Department of
Chemistry, Zhejiang University, Hangzhou 310027, China
Received August 27, 2010; Revised Manuscript Received October 20, 2010
ABSTRACT: Two new chiral two-dimensional coordination networks, ZnL2(H2O)2 (1) and CdL2(H2O)2 (2) [L=1,2,2-
trimethyl-3-(pyridin-4-ylcarbamoyl)cyclopentanecarboxylic acid], have been synthesized and structurally characterized by single
X-ray structure analysis, featuring very unusual interwoven (4,4) square grids of double helices. The frameworks exhibit high
thermal stability as confirmed by thermogravimetric analysis and powder X-ray diffraction studies. The unique chiral networks
attributed to the chiral organic linker have led to their nonlinear optical properties.
Advance DMX500 spectrometer using tetramethysilane (TMS) as
an internal standard. Infrared spectra (IR) were recorded on a
Introduction
The design and synthesis of noncentrosymmetric solid state
materials is one of the most important and challenging goals
ofthechemistry andmaterialsscience community. The unique
functions and properties of such noncentrosymmetric solid
state materials such as second harmonic generation (SHG)
and ferroelectricity are heavily dependent on their framework
structures, so extensive effort to rationalize the structure-
property relationship has been spent over the past two
decades.1-11 Pioneered by Lin,1 previous research on the
nonlinear optical materials has been mainly focused on the
construction of acentric metal-organic coordination poly-
mers (MOCPs) by making use of nonsymmetrical organic
linkers.12-21
The incorporation of chiral organic linkers into the coordi-
nation networks can enforce the construction of noncentro-
symmetric solid state materials and thus induce their non-
linearopticalproperties atwitnessed in the growingnumber of
nonlinear optical chiral coordination networks.22-40 Motivated
by Bu with respect to the design and construction of homochiral
coordination networks fromD-camphoric acid,41-43 we devel-
oped a new chiral and helical organic linker to have both
D-camphor and pyridyl moieties for their coordination to
metal ions and thus the construction of chiral coordination
networks (Scheme 1). Herein, we report two new chiral two-
dimensional (2D) coordination networks, ZnL2(H2O)2 (1)
and CdL2(H2O)2 (2) [L = 1,2,2-trimethyl-3-(pyridin-4-ylcar-
bamoyl)cyclopentanecarboxylic acid], of very unusual inter-
woven (4,4) square grids of double-helix structures exhibiting
nonlinear optical, luminescent, and ferroelectrical properties.
Thermo Fisher Nicolet iS10 spectrometer using KBr pellets. Ele-
mental analyses for C, H, and N were performed on an EA1112
microelemental analyzer. Powder X-ray diffraction (PXRD) pat-
terns were collected in the 2θ = 5-60° range on an X’Pert PRO
˚
diffractometer with Cu KR radiation (λ = 1.542 A) at room
temperature. Thermogravimetric analyses (TGA) were conducted
on a Netszch TGA 209 F3 thermogravimeter with a heating rate of
10/min in an N2 atmosphere. Luminescence spectra for the solid
samples were recorded with a Hitachi F4500 fluorescence spectrom-
eter. The photomultiplier tube voltage was 700 V, and the scan
speed was 240 nm/min. The slit widths were both 2.5 nm for exci-
tation and emission spectra. The second-order nonlinear optical
intensity was estimated by measuring a powder sample 61-90 μm
in diameter relative to KDP. A pulsed Q-switched Nd:YAG laser at a
wavelength of 1064 nm was used to generate second-order harmonic
generation (SHG signals). The backscattered SHG light of 532 nm
was collected and detected with a photomultiplier through a mono-
chromator. The ferroelectric properties of solid state samples are
measured from a powdered sample in the form of a pellet using a
Premier II ferroelectric tester (Radiant Technologies, Inc.) at room
temperature, and the electric hysteresis loop was observed by Virtual
Ground Mode (the measurement is ac, and the frequency is 10 Hz).
X-ray Collection and Structure Determination. Crystallographic
measurements for 1 and 2 were taken on an Oxford Xcalibur
Gemini Ultra diffractometer with an Atlas detector using graphite-
˚
monochromatic Mo KR radiation (λ = 0.71073 A) at 293 K. The
determinations of the unit cells and data collections for the crystals of 1
and 2 were performed with CrysAlisPro. The data sets were corrected
by empirical absorption correction using spherical harmonics,
implemented in the SCALE3 ABSPACK scaling algorithm.45 All
structures were determined by direct methods and refined by the
full-matrix least-squares method with the SHELX-97 program
package.46 All non-hydrogen atoms, including solvent molecules,
were located successfully from Fourier maps and were refined aniso-
tropically. H atoms on C atoms were generated geometrically. The H
atoms of the water molecules and amine groups were clearly visible in
difference maps and were handled in the subsequent refinement with
fixed isotropic displacement parameters. Crystallographic data are
summarized in Table 1, and the selected bond lengths and angles are
listed in Table 2.
Experimental Section
General Procedures. All the chemicals were commercially avail-
able and used without further purification. (1R,3S)-1,2,2-Trimethyl-
cyclopentane-l,3-dicarbonyl chloride (3) was synthesized according
to ref 44. 1H and 13C NMR spectra were recorded on a Bruker
Synthesis of (Z)-1,8,8-Trimethyl-4-(pyridin-4-ylimino)-3-oxabicyclo-
[3.2.1]octan-2-one (4). To the suspension of 4-pyridinamine (7.52 g,
80 mmol) in CH2Cl2 at 0 °C was added (1R,3S)-1,2,2-trimethylcy-
clopentane-1,3-dicarbonyl chloride (3) (4.74 g, 20 mmol) in portions.
*To whom correspondence should be addressed. B.C.: fax, (210) 458-
7428; e-mail, banglin.chen@utsa.edu. G.Q.: fax, (þ86) 571-879-51234;
e-mail, gdqian@zju.edu.cn.
r
2010 American Chemical Society
Published on Web 11/05/2010
pubs.acs.org/crystal

5292 Crystal Growth & Design, Vol. 10, No. 12, 2010
Scheme 1. Synthesis of 1 and 2
Huang et al.
Table 1. Crystallographic Data Collection and Refinement Results for 1
and 2
product, 1,2,2-trimethyl-3-(pyridin-4-ylcarbamoyl)cyclopentane-
carboxylic acid, as a white solid (80% yield): 1H NMR (DMSO) δ
10.06 (s, 1H), 8.41 (d, 2H), 7.59 (d, 2H), 2.92 (t, 1H), 2.46 (m, 1H),
2.04 (m, 1H), 1.76 (m, 1H), 1.42 (m, 1H), 1.19 (s, 6H), 0.78 (s, 3H);
13C NMR (DMSO) δ 177.274, 173.081, 150.776, 146.115, 113.759,
56.139, 54.023, 46.710, 32.656, 23.031, 22.978, 22.209, 21.677; MS
(ESI) exact mass calcd for C15H20N2O3 [M þ H]þ 277.2, found
277.1, [M - H]- 275.2, found 275.0; HRMS (ESI) exact mass calcd
for C15H20N2O3 [M þ H]þ 277.1547, found 277.1540.
1
2
chemical formula
formula weight
temperature (K)
C30H42N4O8Zn
652.05
293(2)
0.71073
monoclinic
C2
19.3447(9)
8.9864(5)
9.2291(5)
95.750(5)
1596.3(1)
2
C30H42N4O8Cd
699.09
293(2)
0.71073
monoclinic
C2
19.8930(7)
9.0654(3)
9.4049(3)
99.598(3)
1672.3 (1)
2
˚
wavelength (A)
crystal system
space group
Synthesis of ZnL2(H2O)2 (1). AmixtureofZnNO3 6H2O (0.0295 g,
˚
3
a (A)
0.1 mmol) and L (0.0552 g, 0.2 mmol), ethanol (2.5 mL), water (2.5 mL),
and DMF (5 mL) were sealedinto a 20 mL Teflon cup. The vesselwas
heated at 120 °C for 2 days. After the mixture had slowly cooled
to room temperature, colorless block crystals were obtained in 80%
yield. Anal. Calcd for C30H42N4O8 [Zn (%)]: C, 55.26; H, 6.49; N,
8.59. Found: C, 55.14; H, 6.51; N, 8.37. IR (KBr, cm-1): 3552(s),
3323(s), 3228(w), 3160(w), 3070(w), 2978(s), 1693(s), 1596(s),
1513(s), 1458(w), 1434(w), 1402(w), 1360(w), 1331(w), 1313(s),
1213(s), 1175(s), 1068(w), 1026(s), 842(s), 781(w), 538(w), 519(w).
Synthesis of CdL2(H2O)2 (2). Complex 2 was prepared via a pro-
˚
b (A)
˚
c (A)
β (deg)
3
V (A )
˚
Z
density (calculated g/cm3)
absorbance
1.357
0.823
1.388
0.704
coefficient (mm-1
)
F(000)
crystal size (mm3)
688
0.34 ꢀ 0.28 ꢀ 0.09
724
0.44 ꢀ 0.34 ꢀ 0.20
goodness of fit on F2
R1, wR2 [I > 2σ(I )]a
R1, wR2 (all data)a
largest difference peak
1.036
1.014
cedure similar to that of 1, except that Cd(NO3)2 4H2O was used
instead of ZnNO3 6H2O (70% yield). Anal. Calcd for C30H42N4O8
3
0.0340, 0.0447
0.0401, 0.0455
0.241, -0.177
0.0203, 0.0410
0.0204, 0.0410
0.252, -0.164
3
[Cd(%)]:C, 51.54;H, 6.06; N, 8.01. Found:C, 51.63;H, 6.09; N, 7.76.
IR(KBr,cm-1): 3535(s), 3371(s), 3235(w), 3163(w), 3077(w), 2976(s),
1690(s), 1598(s), 1511(s), 1430(s), 1360(s), 1311(w), 1213(s), 1176(s),
1126(w), 1018(s), 928(w), 891(w), 839(s), 781(w), 610(w), 535(w),
484(w).
3
˚
and hole (e/A )
P
Table 2. Selected Bond Lengths (angstroms) and Angles (degrees) for
P
P
P
2 1/2
] .
a R1 = (|Fo| - |Fc|)/ |Fo|; wR2 = [ w(|Fo| - |Fc|2)/ wFo
Results and Discussion
1 and 2
The single-crystal X-ray diffraction studies reveal that both
1 and 2 have a 2D polymeric structure crystallizing in mono-
clinic space group C2. As depicted in Figure 1, the Zn(II) center
lies on a crystallographic 2-fold axis and is coordinated to two
pyridyl nitrogen atoms and two carboxylate oxygen atoms
that come from four different L ligands in compound 1. The
bond angles about the Zn tetrahedron range from 96.71(9) to
1a
Zn(1)-O(2)i
1.935(2)
2.060(2)
135.9(1)
O(2)i-Zn(1)-N(1)
O(2)ii-Zn(1)-N(1)
N(1)-Zn(1)-N(1)iii
96.67(9)
110.75(9)
102.5(1)
Zn(1)-N(1)
O(2)i-Zn(1)-O(2)ii
2b
Cd(1)-O(2)i
Cd(1)-O(3)i
Cd(1)-N(1)
2.223(2) N(1)-Cd(1)-N(1)iii
2.470(2) O(2)i-Cd(1)-O(3)i
2.303(2) O(2)ii-Cd(1)-O(3)i
93.8 (1)
54.95(6)
108.81(8)
141.81(8)
91.37(8)
107.3(1)
˚
135.7(1) A and deviate slightly from those of a perfect tetra-
O(2)i-Cd(1)-O(2)ii 155.5(1)
N(1)-Cd(1)-O(3)i
N(1)iii-Cd(1)-O(3)i
O(3)i-Cd(1)-O(3)ii
hedron. The Cd(II) in compound 2 has a slightly different
coordination environment and is six-coordinated to two pyr-
idyl nitrogen atoms and four oxygen atoms from two clelating
carboxylate group. The local coordination geometry about the
Cd(II) center can best be described as a distorted octahedron
with the bond angles ranging from 87.80(8)° to 155.5(1)°.
The most interesting structural features are their chiral and
helical network structures, apparently attributed by the chiral
and helical geometry of the bridging ligand L. Typically,
coordination networks of diamond topology will be self-
assembled from such pyridylcarboxylate organic linkers as
exemplified in Lin’s works.1 Here the bend and helical nature
of organic linker L have led to the formation of the 2D (4,4)
wavelike grids that are interwoven with each other to occupy
the large void space within the wavelike grids (Figure 2a).
It should be noted that right-handed double-helical chains
O(2)i-Cd(1)-N(1)
O(2)ii-Cd(1)-N(1)
87.80(8)
109.18(8)
a For 1: (i) -x þ 1, y þ 1, -z - 1; (ii) x, y þ 1, z þ 1; (iii) -x þ 1, y, -z.
b For 2: (i) -x þ 1, y þ 1, -z - 1; (ii) x, y þ 1, z þ 1; (iii) -x þ 1, y, -z.
The solution was allowed to stir at 0 °C for 5 h and then warmed to
room temperature and allowed to stir overnight. Silica gel column
chromatography with an eluent of ethyl acetate and dichloromethane
(1:1, v/v) afforded a pure white solid (2.58 g, 50% yield): 1H NMR
(CDCl3) δ 8.49 (d, 2H), 6.82 (d, 2H), 2.90 (t, 1H), 2.32 (m, 1H), 2.13
(m, 1H), 1.99 (m, 2H), 1.25 (s, 3H), 1.15 (s, 3H), 1.05 (s, 3H).
Synthesis of 1,2,2-Trimethyl-3-(pyridin-4-ylcarbamoyl)cyclo-
pentanecarboxylic Acid (L). A mixture of (Z)-1,8,8-trimethyl-
4-(pyridin-4-ylimino)-3-oxabicyclo[3.2.1]octan-2-one and triethyla-
mine (1 mL) was stirred at 50 °C in water for 24 h. The precipitate was
filtered off, and the filtrate was removed in vacuo to give the crude

Article
Crystal Growth & Design, Vol. 10, No. 12, 2010 5293
Figure 1. ORTEP drawing (with thermal ellipsoids at 50% probability) showing the coordination environment of the metal site in 1 (a)
and 2 (b).
Figure 2. (a) Perspective views of the single (4,4) wavelike grid constructed from double right-handed helices. (b) Space filling and perspective
views of one right-handed helix along the b axis. Color code: Zn, azury; oxygen, red; nitrogen, blue.
Figure 3. Schematic showing the parallel arrangement of (a) double
right-handed helices and (b) 2D interwoven grids in a staggered
arrangement.
Figure 5. TGA curves for 1 and 2 under nitrogen.
21-helicalchains alongthe b axisin bothstructures. Theperiod
˚
of helical chains is 17.973 A, as the double of the b parameter
of the unit cell. These double helices are in an orderly arrange-
ment with the zinc or cadmium atoms functioning as hinges
to result in a homochiral 2D sheet (Figure 3). To the best
of our knowledge, coordination networks 1 and 2 are the first
example of MOCPs exhibiting such unique interwoven (4,4)
square grids of double-helix structures. These interwoven (4,4)
square grids of double helices are alternately stacked in ABAB
packing (Figure 4)
Figure 4. Packing diagrams of compound 1 of the ABAB sequence
Bothcompounds 1and 2exhibit quitehighthermalstability
with views along (a) the c axis and (b) the b axis.
as shown in thermogravimetric analysis (TGA) (Figure 5).
(Figure 2b) are distinguishable in the (4,4) network along the
b axis. Because the right-handed helix of the L is predetermined
by the R-c and S-c in the ligand, the coordinated tetrahedron
for Zn or the octahedron for Cd would only form the right-
handed forms and thus induces the absolute right-handed
For 1, theTGA curve shows the weight loss of interlayerwater
molecules (calculated, 5.15%; observed, 4.94%) in the tem-
perature range of 100-175 °C. The host framework is stable
up to ca. 316 °C. For 2, the TGA curve shows the weight loss
of interlayer water molecules (calculated, 5.52%; observed,

5294 Crystal Growth & Design, Vol. 10, No. 12, 2010
Huang et al.
Figure 7. Photoluminescence spectra of 1 (red), 2 (blue), and L
(black) in the solid state at room temperature.
Figure 6. PXRD patterns of 1 and 2 (calculated, black; as-synthe-
sized, blue; activated at 180 °C in vacuum for 12 h, red).
Figure 8. Electronic hysteresis loops of powdered samples in the
form of pellets of 1 using a Premier II ferroelectric tester at room
temperature.
5.39%) in the temperature range of 100-145 °C. The host
framework is stable up to ca. 316 °C. The powder X-ray
diffraction patterns (PXRD) of dehydrated samples 1 and 2
(after removal of guestwater molecules as the sample is heated
to 180 °C in vacuum) indicate that the host framework
also matches those of the pristine samples, suggesting their
structures are intact after removal of solvent water molecules
(Figure 6).
Weconductedthe quasi-Kurtz secondharmonic generation
(SHG) measurements on powdered samples to confirm their
acentricity as well as to evaluate their potential application
as second-order NLO materials.47 Preliminary experimental
results indicate that both 1 and 2 display SHG efficiencies
that are approximately 2.8 and 2.6 times that of KDP, respec-
tively. The modest powder SHG response of 1 and 2 may be
attributed to a comparable short donor-acceptor system,
which is essential for second-order optical nonlinearity. How-
ever, their SHG responses are systematically stronger than
those 2D coordination networks containing a comparable
length donor-acceptor system,1,13,19,48 indicating the obvious
effects of the chirality and helices on SHG efficiency.
The photoluminescence spectra of 1 and 2 were investigated
in the solid state at room temperature (Figure 7). Upon
excitation of 1 and 2 at 365 nm, intense bands in the emission
spectra are observed at 437 nm for 1 and 440 nm for 2. This
emission can be attributed to the intraligand emission from L.
Free L exhibits a luminescence at ca. 453 nm upon excita-
tion at 365 nm in the solid state at room temperature. The
enhancement and blue shift (from ca. 453 to 437 nm) of the
emission of the L in 1 compared to that of free ligand may be
attributed to the coordination bond between the ligand and
Zn(II), which increases the rigidity of the ligand and reduces
the loss of energy by radiationless decay of the intraligand
emission excited state.12,49
Compounds 1 and 2 both crystallize in space group C2,
which belongs to one of the 10 polar point groups (C1, Cs,
C2, C2v, C4, C4v, C3, C3v, C6, and C6v).7,17,50,51To detect the
ferroelectricity, the hysteresis loops of electric polarization
weremeasured on a powdered sampleof1 (Figure 8). Atroom
temperature, the remnant polarization (Pr) is ca. 0.1280 μC/
cm2 for 1 with a coercive field (Ec) of ca. 12 kv/cm. Saturation
of the spontaneous polarization (Ps) in 1 occurs at 0.25 μC/
cm2, which is the same as a typical ferroelectric compound
(e.g., NaKC4H4O6 4H2O, Rochelle salt; usually Ps = 0.25 μC/
3
cm2), but much smaller than that found in KDP (≈5 μC/cm2).
In conclusion, the incorporation of a new chiral and helical
organic linker has led to two novel coordination networks
of unique interwoven (4,4) square grids of double-helix struc-
tures, exhibiting nonlinear optical properties. The power
to synthesize a variety of chiral and helical organic linkers
with typical binding sites such as carboxylate and pyridyl
groups for their coordination with metal ions and/or metal-
containing clusters has provided the promise to construct a
series of novel chiral and helical coordination networks of
diverse structures; thus, some novel functional nonlinear
optical coordination networks will be emerging in the future.
Acknowledgment. This work was supported by the National
Natural Science Foundation of China (Grants 50625206,

Article
Crystal Growth & Design, Vol. 10, No. 12, 2010 5295
50928201, 50972127, and 51010002), Grant CHE 0718281
from the National Science Foundation, and Grant AX-1730
from the Welch Foundation (B.C.).
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Supporting Information Available: X-ray data of 1 and 2 in CIF
format and figures of asymmetric units. This material is available
free of charge via the Internet at http://pubs.acs.org.
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