Supramolecular Interactions Induced Chirality Transmission, Second Harmonic Generation Responses, and Photoluminescent Property of a Pair of Enantiomers from in Situ [2 + 3] Cycloaddition Synthesis

Article abstract of DOI:10.1021/acs.cgd.5b01684

Spontaneous resolutions from an in situ reaction especially for a Sharpless reaction are really rare. Here we display a new pair of enantiomeric compounds Δ- and Λ-[Mn(4-tzba)(bpy)₂·H₂O](bpy)·3H₂O (labeled as Δ-1 and Λ-1 respectively) (4-tzba = 4-tetrazolbenzoic acid; bpy = 2,2′-bipyridine) from a Sharpless reaction. They crystallized in the P2₁2₁2₁ chiral space group and demonstrated strong second harmonic generation (SHG) responses and red photoluminescence property. The chiral metal conformations were captured by the introduction of the distorted bpy and the in situ synthesized 4-tzba ligands. The hydrogen bonds connecting the 4-tzba and central metal play a crucial role in the chirality transmission, as well as the donor-acceptor type SHG nonlinear response.

Full text of DOI:10.1021/acs.cgd.5b01684

Article
pubs.acs.org/crystal
Supramolecular Interactions Induced Chirality Transmission, Second
Harmonic Generation Responses, and Photoluminescent Property of
a Pair of Enantiomers from in Situ [2 + 3] Cycloaddition Synthesis
Ji-Xing Gao, Jian-Bo Xiong, Qing Xu, Yu-Hui Tan, Yi Liu, He-Rui Wen, and Yun-Zhi Tang*
School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou, 341000, Jiangxi Province, P.
R. China
S
* Supporting Information
ABSTRACT: Spontaneous resolutions from an in situ reaction especially for a
Sharpless reaction are really rare. Here we display a new pair of enantiomeric
compounds Δ- and Λ-[Mn(4-tzba)(bpy)2·H2O](bpy)·3H2O (labeled as Δ-1 and Λ-1
respectively) (4-tzba = 4-tetrazolbenzoic acid; bpy = 2,2′-bipyridine) from a Sharpless
reaction. They crystallized in the P212121 chiral space group and demonstrated strong
second harmonic generation (SHG) responses and red photoluminescence property.
The chiral metal conformations were captured by the introduction of the distorted bpy
and the in situ synthesized 4-tzba ligands. The hydrogen bonds connecting the 4-tzba
and central metal play a crucial role in the chirality transmission, as well as the donor−
acceptor type SHG nonlinear response.
an enantio-pure ligand to translate the same handedness to the
final framework; (ii) using a chiral precursors in the presence of
chirality inducing agents such as chiral additives, chiral solvents,
or chiral catalysts; (iii) spontaneous resolution during the
crystallization from nonchiral starting materials.17−21 All three
methods have their advantages and drawbacks; spontaneous
resolution requires the generation of a chiral source which can
transmit the stereochemical information. If there are prefer-
ential and extended homochiral interactions between a chiral
source and its neighbors, the chirality would be able to extend
to a higher dimensionality. The source of chirality may arise
from the distorted coordination geometry of the central metals,
the twisted conformation of the ligands, the supramolecular
interactions, or a combination thereof; the targeted control of
the resulting chirality is very difficult, and in some cases chiral
agents are needed as reaction media, templates, or auxiliary
ligands to induce chirality in the resulting structures.22−26
It is inspiring that we recently synthesized the first
enantiomers of metal tetrazole compound ([Cu(Tzmp)]n, 2)
from in situ [2 + 3] cycloaddition reactions of a organic nitrile
ligand with sodium azide in the presence of Cu2+ as a Lewis
acid.27 In 2, the chirality originates in the chiral central copper
atoms which is similar to the chiral carbon atoms in organic
compounds. Tong et al. have discovered that axially chiral
moieties of bpy can be isolated from the rotation of the two
pyridine rings via spontaneous resolution.28 As an ongoing
INTRODUCTION
■
Chiral or non-centrosymmetric compounds are particularly
interesting as their potential applications in the areas of
information technology, optical storage, asymmetric catalysis,
and chiral separation.1−6 Especially, second order nonlinear
optical (NLO) materials have been receiving increasing
attention because of their wide applications in areas including
telecommunications, electric-optical devices, light modulators,
and information storage. Traditionally, studies of second-order
NLO materials were mainly focused on inorganic materials,
such as quartz, potassium dihydrogen phosphate (KDP),
lithium niobate (LiNbO3), etc.1−11 However, they usually
suffer a lot of drawbacks such as with low NLO responses,
difficulty to synthesize, lack of optical quality, and slow electro-
optic response times. Inorganic−organic hybrid materials have
emerged in the past few years as promising candidates for NLO
materials.1,12−15 These compounds usually combine high
nonlinear optical coefficients of the organic molecules with
excellent physical properties of the inorganic material. The
coordination of organic ligands to metal ions can not only give
rise to metal-to-ligand charge transfer transitions, but also allow
the organic chromophores to be arranged in orderly geo-
metries, enabling multidirectional charges transfer and exhibit-
ing interesting photoluminescence properties.2,16
However, the rational design and synthesis of inorganic−
organic hybrid frameworks with chiral or acentric structures has
proven to be a most challenging and laborious task because
most hybrid frameworks are inclined to crystallize in a
symmetric space group. It is well-known that three general
methods are used to assemble homochiral complexes: (i) using
Received: November 28, 2015
Revised: January 13, 2016
© XXXX American Chemical Society
A
DOI: 10.1021/acs.cgd.5b01684
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Article
effect to obtain the homochiral compounds and analyze the
mechanism of spontaneous resolution, we attempt to construct
some new types of enantiomers from a [2 + 3] cycloaddition
reaction by other supramolecular interactions.
Inspired by the previous work, we performed the Sharpless
reaction of bpy, 4-tzba, sodium azide, and manganese acetate
and obtained a new pair enantiomers from the [2 + 3]
cycloaddition reaction. Here we detail their spontaneous
resolution, crystal structures, circular dichroism (CD) spectra,
second harmonic generation (SHG) responses, and photo-
luminescent properties.
Table 1. Crystal Data and Structure Refinement for Δ-1 and
Λ-1
compound
Δ-1
Λ-1
empirical formula
formula weight
temperature (K)
crystal system
space group
a (Å)
C38H36MnN10O6
783.71
C38H36MnN10O6
783.71
293(2)
293(2)
orthorhombic
P212121
orthorhombic
P212121
10.9122(4)
14.8109(6)
23.2500(9)
3757.7(3)
0.412
10.9802(4)
14.8405(6)
23.2117(10)
3782.4(3)
0.409
b (Å)
c (Å)
V (Å3)
EXPERIMENTAL SECTION
■
μ (mm−1
)
Synthesis. All reagents were purchased from commercial sources
and used as received. Hydrothermal treatment of 4-tzba (0.0147 g, 0.1
mmol), NaN3 (0.0195 g, 0.3 mmol) (Caution: Metal azides may be
explosive), bpy (0.0468 g, 0.3 mmol), and Mn(CH3COO)2·H2O
(0.0382 g, 0.2 mmol) in a mixed solution of ethanol (0.5 mL) and
water (2 mL) at 140 °C for 3 days give two different crystals: one is
deep yellow block crystals (Δ-1), and the other (Λ-1) appears pale
yellow with needle shapes (Figure S1 and Scheme 1). Yield: 0.0569 g,
D
Z
calc/M gm−3
1.385
1.376
4
4
F(000)
1628
1628
Flack parameter
GOF
−0.009(8)
1.010
0.003(11)
1.005
R1/wR2 [I > 2σ(I)]
Δρmax/Δρmin (e·Å−3
0.0511/0.0820
0.832/−0.433
0.099/0.0813
0.194/−0.259
)
Scheme 1. Preparation of Complex
from KBr pellets in the range of 400−4000 cm−1 on a Bruker
TENSOR27 spectrometer. Powder X-ray diffraction patterns were
recorded on a D8 ADVANCE diffractometer with Cu Kα radiation at a
scanning rate of 4° min−1 with 2θ ranging from 5° to 50°. PL emission
spectra were measured at room temperature using a spectra
fluorophotometer (JASCO, FP-6500) with a xenon lamp (150 W)
as a light source. The solid state CD spectra were recorded on a Jasco-
1500 circular dichroism spectropolarimeter at 293 K. The CD spectra
were measured on the resulting complexes as crystals (ca. 0.4 mg) in
100 mg of oven-dried KBr. Spectra were recorded for the wavelength
range 250−700 nm; for all the disks the path length was 0.3 mm. The
SHG response was measured on powdered sample by using the
experimental method adapted from that reported by the Kurtz−Perry
method. An unexpanded laser beam with low divergence (pulsed
Nd:YAG at a wavelength of 1064 nm, 5 ns pulse duration, 1.6 MW
peak power, 10 Hz repetition rate) was used. The instrument model is
FLS 920, Edinburgh Instruments, while the laser is Vibrant 355 II,
OPOTEK.34 Thermogravimetric analysis data were recorded on a
PerkinElmer TGA 4000 instrument in the temperature range of 303−
1073 °C under an N2 atmosphere. Differential scanning calorimetry
was carried out on a TA Q2000 DSC instrument in the temperature
range 340−870 K under nitrogen at atmospheric pressure in
aluminum crucibles with a heating rate of 10 K/min. The single-
crystal samples with silver painted as the electrodes were used for
dielectric studies, and dielectric permittivity ε (ε = ε′ − iε″) was
measured on a Tonghui TH2828A over the frequency range of 2 kHz
to 1 MHz and in the temperature range from 170 to 340 K with the
measuring ac voltage fixed at 1 V (a high voltage may puncture the
samples).
72.6%, C38H36N10O6Mn (783.71). Calcd for 1 (1 = the mixture of Δ-1
and Λ-1): C, 58.24; H, 4.63; N, 17.87. Found: C, 58.32; H, 4.61; N,
17.79. IR (KBr, cm−1): 3420(m), 1601(s), 1556(m), 1441(m),
1380(s), 1145(w), 1011(m), 758(s). Comparing the IR spectra of
complex 1 and 4-tzba, a serial of new strong peaks ranging from 1601
to 1441 cm−1 appear, while the absorption of cyano group at 2355
cm−1 Vas(CN) and Vs(CN) and the azide group in 2100 cm−1
disappear in 1 (Figure S2), indicating that the [2 + 3] Sharpless
reaction between cyano group and azide anion has finished.10,29,30 The
powder X-ray diffraction further conformed the phase purity (Figure
S3).
Crystallography. We collected X-ray single-crystal diffraction data
for Δ-1 and Λ-1 on a Bruker P4 diffractometer with Mo Kα radiation
(λ = 0.71073 Å) at 298 K using the θ-2θ scan technique and corrected
them by Lorentz−polarization and absorption corrections.31,32 Both
crystal structures were solved by direct method and refined by the full-
matrix method based on F2 by means of the SHELXLTL software
package.33 Non-H atoms were refined anisotropically using all
reflections with I > 2σ(I). All H atoms were generated geometrically
and refined using a “riding” model with Uiso = 1.2Ueq (C). The small
Flack parameters for Δ-1 (−0.009(8)) and Λ-1 (0.003(11)) clearly
indicate that the absolute structure is correctly assigned in each case.33
The asymmetric units and the packing views were drawn with
DIAMOND (Brandenburg and Putz, 2005). Angles between some
planes were calculated using DIAMOND, and other calculations were
carried out using SHELXLTL. Crystal data and structures refinement
for Δ-1 and Λ-1 are listed in Table 1. Their selected intra-atomic
distances and bond angles are given in Table S1. Copies of this
information can be obtained free of charge from The Director, CCDC,
12 Union Road, Cambridge, CB2 1EZ, UK. Fax (int. code)
−44(1223)336−033 or E-mail: deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.ck). CCDC No. for Δ-1, 1438511 and for Λ-1,
1438510.
RESULTS AND DISCUSSION
■
Crystal Structures. Single crystal X-ray diffraction analyses
reveal that 1 contains Δ-1 and its enantiomorph Λ-1 with the
same chiral space group of P212121, suggesting that
spontaneous resolution occurred. The Flack absolute structure
parameters33 (Table 1) further verify their chirality. As shown
in Figure 1a, Δ-1 and Λ-1 have perfect mirror image; herein we
only detailed the structure of Δ-1. The fundamental building
unit of Δ-1 consists of one Mn(II) ion, one 4-(5H-tetrazol-5-
yl)benzoic acid ligand, two coordinated bpy molecules, one
lattice bpy molecule, one coordinated H2O molecule, and three
lattice H2O molecules (Figure 1). The central Mn(II) adopts a
hexa-coordinated octahedral geometry surrounded by four
nitrogen atoms from two chelating bpy molecules, one oxygen
Physical Techniques. Elemental analyses (CHN) were carried out
on a Vario EL III elemental analyzer. FT-IR spectra were recorded
B
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Article
Figure 1. (a) View of the coordination environment of Mn(II) in Δ-1 (1-P, left) and Λ-1 (1-M, right) and the axially chiral conformations of bpy
and the angle between two pyridine rings. (b) hydrogen-bonded right and left helix in Δ-1 and Λ-1.
Figure 2. (a) View of the hydrophilic layer constructed by array of the tubular channels (pink area) and P helix in Δ-1. (b) Packing view along the a-
axis and π−π interactions in Δ-1 (the red dashed line indicates hydrogen bonds). (c) π−π interactions between free bpy and coordinated bpy
ligands.
C
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Article
Figure 3. (a) Solid state UV absorption spectrum of 1; (b) 10 groups of solid-state CD spectra of Δ-1 and Λ-1 show the opposite Cotton effects.
Figure 4. (a) Oscillo scopetraces of SHG signals for the powder of 1 (b) solid state fluorescent emission spectrum.
atom from 4-tzba, and one coordinated water molecule,
respectively. All the Mn−N and Mn−O distances ranged
from 2.262(13) to 2.292(12) Å and 2.075(11) to 2.149(13) Å,
respectively (Table S1), which are similar to the other
analogous compounds.35,36 There are two chelating bpy
molecules coordinated to the central metal; normally, bpy is
achiral because of its rigid π−π conjugated structure between
two pyridyl rings. However, it becomes an important element
of chirality in 1, in that the two axially chiral conformations of λ
and δ are “locked”. The dihedral angle between two pyridyl
planes is 12.41° (for Λ-1 it is 13.17°) in one of the bpy, and the
other one is still coplanar28 (Figure 1b). In our previous work,
we have reported other enantiomers of metal tetrazole
compound ([Cu(Tzmp)]n, 2) from in situ [2 + 3] cyclo-
addition reactions;27 however, they have totally different chiral
sources. Complex 2’s chirality comes from the chiral central
copper atoms which can be viewed as the chiral carbon atoms
in organic compounds, while compound 1’s chirality originates
from axially chiral conformations of bpy. As far as we know,
although a lot of metal tetrzole complexes have been reported
before, the spontaneous resolutions’ cases from in situ [2 + 3]
cycloaddition reactions are very rare.
hydrogen bonds O(2W)−H(2WB)···N(8)#3 (2.785(2) Å)
and O(1W)−H(1WB)···O(2W) (2.667(2) Å) (Table S2)
combined with central metals to form an elegant right-handed
P helix (for Λ-1, left-handed M helix) running along the 21
screw axis with the pitch equal to 10.91 Å (for Λ-1, 10.98 Å).
The remarkable feature of P212121 space group is the existence
of 21 screw axes.22 The neighboring helices are fused side-by-
side through H-bonds between the tetrazole rings and lattice
water molecules (O(3W)−H(3WB)···N(7)#1, 2.873(2) Å and
O(2W)−H(2WB)···N(8)#3, 2.785(2) Å) to form a layer
parallel to the ab plane, generating chiral tubular channels
running along the a-axis (Figure 2a). All in all, the hydrogen-
bonding helices and channels formed the hydrophilic layer in
the ab plane. The 2D sheets are further involved by π−π
interactions to realize a 2D → 3D antiparallel network along
the c-axis, as depicted in Figure 2b. By virtue of the free bpy
molecule, two π−π interactions are found with the distances
being 3.789 and 4.071 Å (weak effect, Figure 2c), respectively.
Thus, the lattice bpy molecule not only has a space-filling role
in the material but also directs the formation of the whole
framework. We have been unable to remove it without causing
the structure to collapse. Generally speaking, the structural
chirality of the central metals can be transferred to the whole
polymeric framework via the supermolecular interactions.
To confirm the optical activity and enantiomeric nature of Δ-
1 and Λ-1, the solid-state CD spectra were recorded on their
single crystals (Figure 3 and Figure S4). The UV absorption
spectra of 1 in the region 236−280 nm showing two strong
Though the metal coordination number and coordination
sphere geometry are crucial factors to generate chirality,
another significant factor is an efficient transfer of chiral
information from the achiral unit to a supramolecular structure
through noncovalent interactions that simultaneously form
homochiral helices.17−21,37−39 In Δ-1, the intermolecular
D
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Article
peaks at 236 and 280 nm (Figure 3a) respectively are attributed
to the d−d transition of Mn2+ ions and the ligand to metal
charge transition (LMCT) in which the lone pair electrons of
oxygen are transferred to the unoccupied d orbital of Mn2+
ions.40,41 The further experiment confirmed that the UV
absorption peaks appear in the region 266 and 316 nm for bpy
ligand and 298 and 362 nm for 4-tzba ligand respectively
(Figure S5), far way from 236 and 280 nm. It should be noted
that we have proven by experiment that the solid state UV
absorption spectra of Δ-1 and Λ-1 are totally in line with that
of 1. Hence, the CD spectrum for Δ-1 with yellow block
morphology exhibits a negative Cotton effect at λmax = 315 nm,
indicating that the bulk sample is enantio enriched (Figure
3b).42 The origin of chirality of compound Δ-1 should be
closely related to the central chirality from the distortion of one
chelating bpy molecule and the 21 screw axes with the same
handedness assembled from the hydrogen bonds. In compar-
ison, the CD spectrum of Λ-1 with pale yellow and needle
shapes shows the opposite CD signals at similar wavelengths.
Nonlinear Optical and Photoluminescence Properties.
A general method to judge weather compounds are non-
centrosymmetric or homochiral is to measure their nonlinear
optical properties. Thus, the solid-state SHG response of 1 was
conducted at room temperature. As we expected, compound 1
shows a strong SHG signal (Figure 4a); the intensity (0.172) is
close to (0.75 time) that of KDP (0.206) with the same test
condition, indicating it may have potential applications in NLO
materials. The reason may be attributed to the introduction of
the distorted bpy and the in situ synthesized 4-tzba. Then, the
hydrogen bonds connecting the 4-tzba and central metals play a
crucial role in the donor−acceptor type SHG nonlinear
response.
The solid-state luminescent emission spectra of 1 were
studied at room temperature (Figure 4b). The emission peak at
706 nm under the excitation of 468 nm43−45 is produced by
octahedrally coordinated manganese, and the emissive lifetime
is 0.446 ms according to the fitted curve of 1 (Figure S6a). The
emission at 706 nm is attributable to the (t2g)3(eg)2−(t2g)4(eg)1
electronic transition,43−45 since luminescent emission from
ligand to ligand change transition of tetrazole complexes mainly
occurs in the arrange of 400−550 nm (in our case, it is 513 nm,
Figure S6b);46−48 meanwhile, the luminescent emission of bpy
appears in 530 nm (Figure S6b). What is more, we have
confirmed through experiment that the solid state fluorescent
spectra of Δ-1 and Λ-1 are totally coincident with that of 1. To
the best of our knowledge, Mn2+ ions with the d5 electronic
configuration have also been used to construct SHG-active
materials. A donor−acceptor type of molecule often possesses
both a large transition moment and a large excited state dipole
moment; in 1, the 4-tzba ligand can be regarded as a good
donor-π-acceptor system (donor = tetrazole ring and acceptor
= carboxylate group).1,30,49
Figure 5. Thermogravimetric analyses (TGA) and DSC curves of 1,
inset: dielectric properties for 1 measured as a function of temperature
under different frequencies.
7.1% weight loss was assigned to the removal of free water
molecules (calcd. 6.9%) which identified well with the
abnormal peak around 390 K of the dielectric constant. What
is more, the dielectric constant peak values are frequency-
dependent; the higher the frequency, the lower the dielectric
constant. Interestingly, the DSC endothermic peak correspond-
ing to the loss of free water molecules possesses a hysteresis of
10 K (400 K); this is because the successive endothermic
process of leaving water molecules postponed the signal
detection. The large endothermic value (217.8 J/g) in turn
proved the strong hydrogen bonding effects of free water
molecules. The successive three-step weight-loss (calcd. 86.1%)
between 420 and 800 K indicates the structural decomposition
and removal of the coordinated ligands were successive and
synchronous. The distinct exothermic peak at 630 K should be
attributed to the decomposition of tetrazole group, which can
release lots of energy (198.5 J/g).55,56 The residue of the
compound is calculated to be Mn (exper. 7.0%, calcd. 7.01%).
CONCLUSIONS
■
We have synthesized another new pair of enantiomeric
tetrazole compounds by using in situ [2 + 3] cycloaddition.
The chirality was captured by the coordination of the distorted
bpy and further extended along the homochiral helices which
are constructed from intermolecular hydrogen bonding. The
CD spectrum study confirmed the spontaneous resolution
process. The strong SHG response signal suggests they are
possible potential NLO materials.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.5b01684.
■
S
Thermogravimetric (TG), Differential Scanning Calo-
rimetry (DSC), and Dielectric Behaviors. Weight loss along
with a varied temperature can be demonstrated by TG analysis,
a thermal signal from a structure phase transition can be
detected by DSC measurements, and the dielectric constant
(ε′) abnormal originated from structural transition or
composition loss can be captured by a temperature-dependent
dielectric constant curve.50−54 Since 1, Δ-1, and Λ-1 have the
same curves for their characterizations of TGA, DSC and
dielectric constants. Here we just described the curves of 1 at
length. As depicted in Figure 5, the first slope at 390 K with
IR spectra, illustration of crystals, powder X-ray
diffraction patterns (PDF)
Accession Codes
CCDC 1438510−1438511 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
E
DOI: 10.1021/acs.cgd.5b01684
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
(28) Liu, J.-L.; Bao, X.; Leng, J.-D.; Lin, Z.-J.; Tong, M.-L. Cryst.
Growth Des. 2011, 11, 2398.
(29) Tang, Y.-Z.; Zhou, M.; Huang, J.; Tan, Y.-H.; Wu, J.-S.; Wen,
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: tangyunzhi75@163.com.
H.-R. Inorg. Chem. 2013, 52, 1679.
(30) Ye, Q.; Li, Y.-H.; Song, Y.-M.; Huang, X.-F.; Xiong, R.-G.; Xue,
Z. Inorg. Chem. 2005, 44, 3618.
(31) Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal Structure
Notes
The authors declare no competing financial interest.
Determination; Universitat of Gottingen: Gottingen, Germany, 1997.
̈
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̈
ACKNOWLEDGMENTS
(32) Sheldrick, G. M. SHELXS-97, Program for Crystal Structure
Solution; Universitat of Gottingen: Gottingen, Germany, 1997.
■
̈
̈
̈
This work was funded by the National Natural Science
Foundation of China (Grant Nos. 21261009, 21471070 and
21461010), Young Scientist Foundation of Jiangxi Province and
Jiangxi Province Science and Technology Support Program
(20133BBE50020), and the Sustentation Fund of Education
Department from Jiangxi Province (GJJ13434).
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F
DOI: 10.1021/acs.cgd.5b01684
Cryst. Growth Des. XXXX, XXX, XXX−XXX