Different conjugated system Zn(II) Schiff base complexes: Supramolecular structure, luminescent properties, and applications in the PMMA-doped hybrid materials

Article abstract of DOI:10.1039/c6dt04159k

A series of Zn(ii) complexes with different conjugated systems, [ZnL¹Cl₂]₂ (Zn1), [ZnL²Cl₂] (Zn2), [Zn(L³)₂]·(ClO₄)₂ (Zn3), [Zn₂L⁴Cl₄] (Zn4), and [ZnL⁵Cl₂] (Zn5), were synthesized and subsequently characterized via single crystal X-ray diffraction, ¹H and ¹³C NMR, FT-IR, elemental analyses, melting point, and PXRD. The X-ray diffraction analyses revealed that the supramolecular frameworks of complexes Zn1-Zn5 are constructed by C-H?O/Cl hydrogen bonds and π?π interactions. Complexes Zn1-Zn3 feature 3D 6-connected {4¹²·6³} topological structures, whereas complex Zn4 exhibits a 3D 7-connected supramolecular framework with a {4¹⁷·6⁴} topological structure. However, complex Zn5 shows one-dimensional "wave-like" chains. Based on these varied structures, the emission maximum wavelengths of complexes Zn1-Zn5 can be tuned in a wide range of 461-592 nm due to the red shift direction of λ_em caused by different conjugated systems and their electron donating abilities. Complex Zn3 shows a strong luminescence in the solid state and in the acetonitrile solution. Therefore, a series of Zn3-poly(methylmethacrylate) (Zn3-PMMA) hybrid materials were obtained by controlling the concentration of complex Zn3 in poly(methylmethacrylate) (PMMA). At an optimal concentration of 4%, the doped polymer film of Zn3-PMMA displays strong green luminescence emissions that are 19-fold in the luminescence intensities and 98 °C higher in the thermal stability temperature compared to the Zn3 film.

Full text of DOI:10.1039/c6dt04159k

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Volume 45 Number
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January 2016 Pages 1–398
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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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ARTICLE
Different Conjugated System Zn(II) Schiff Base Complexes:
Supramolecular Structure, Luminescent Properties and
Application in PMMAꢀDoped Hybrid Material
Received 00th January 20xx,
Accepted 00th January 20xx
YuꢀWei Dong, RuiꢀQing Fan,* Wei Chen, HuiꢀJie Zhang, Yang Song, Xi Du, Ping Wang, LiꢀGuo Wei, and
YuꢀLin Yang,*
DOI: 10.1039/x0xx00000x
www.rsc.org/
1
2
A series of Zn(II) complexes with different conjugated system, [ZnL Cl
2
]
2
(Zn1), [ZnL Cl
2
] (Zn2),
3
4
5
[
Zn(L )
2
]·(ClO
4
)
2
(Zn3), [Zn
2
L Cl
4
] (Zn4), [ZnL Cl
2
] (Zn5) have been synthesized and subsequently
1
13
characterized by single crystal X–ray diffraction, H and C NMR, FT–IR, elemental analyses, melting point,
and PXRD. The Xꢀray diffraction analyses revealed that the supramolecular frameworks of complexes Zn1–
Zn5 are constructed by C−H···O/Cl hydrogen bonds and π···π interactions. Complexes Zn1–Zn3 feature 3D
12
3
6
ꢀconnected {4 ·6 } topology structures, while complexes Zn4 exhibits 3D 7ꢀconnected supramolecular
17
4
framework with {4 ·6 } topology structure. Complex Zn5 shows oneꢀdimensional “waveꢀlike” chains. Based
on these varied structure, the emission maximum wavelengths of complexes Zn1–Zn5 can be tuned in a large
range of 461–592 nm due to the red shift direction of λem causing by different conjugated system and their
electron donating ability. Specially, complex Zn3 shows strong luminescence in the solid state and acetonitrile
solvent. Therefore, a series of Zn3ꢀpoly(methylmethacrylate) (Zn3ꢀPMMA) hybrid materials are obtained
through controlling the concentration of complex Zn3 in poly(methylmethacrylate) (PMMA). At a optimical
concentration of 4%, the doped polymer film of Zn3ꢀPMMA displays a strong and green luminescence
emissions, which is 19ꢀfold in the luminescence intensities and 98 ºC higher in the thermal stability
temperature
compared
with
that
of
Zn3.
Introduction
Even since the discovery of supramolecular chemistry, the chemistry construction of ordered supramolecular architectures. Schiff base
1−5
of noncovalent interactions has experienced tremendous growth. It ligands are frequently used in coordination chemistry due to their
2
2−25
has been applied in many research fields with important implications significant ability to form stable complexes with metalions.
Zinc
in chemistry, physics, material science, engineering and Schiff base complexes with luminescent properties can be used in
6
−15
medicine.
Since the incorporation of wellꢀordered structural applications involving fabrication of novel materials and as probes in
2
6−31
components into a crystal lattice may lead to new advanced materials biological systems.
Controllable tuning of fluorescent properties
with designed physicoꢀchemical properties, such work will provide a of zinc complexes based on ligand design is always a challenge for
foundation for the understanding of how molecules can be organized chemists. From the viewpoint of molecular and crystal engineering,
and how functions are revealed. Meanwhile, many efforts have been the critical criterion for ligand design is how to embed noncovalent
devoted to the use of supramolecular contacts, such as hydrogen interaction groups to control the molecular structure and the
bonds, π···π, C−H···π, aromatic ring···halogen, and/or other van der supramolecular framework.
1
6−21
Waals interactions,
which play important roles in the
Schiff base complexes doped with PMMA as a high performance
32
luminescent materials are rare. What’s more, the idea that greenish
luminescence Schiff base complexes doped with PMMA using in
plastic greenhouses could increase leaf photosynthesis has never
been reported. Polymerꢀdoped systems have obvious technical
advantages, such as flexibility and prominent processing ability,
MIIT Key Laboratory of Critical Materials Technology for New Energy
Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin
Institute of Technology, Harbin 150001 (P. R. China) Eꢀmail:
3
3,34
fanruiqing@hit.edu.cn, ylyang@hit.edu.cn; Fax:+86ꢀ451ꢀ86418270
which are important for optical fibers and fiber amplifiers.
In
Electronic Supplementary Information (ESI) available: Xꢀray crystallographic
recent years, polymerꢀdoped systems are mainly on the rare earth
complexes doped with PMMA, however, the lower synthetic yields,
higher costs, larger doping amount and single luminous color restrict
1
13
files, CCDC 1508968–1508972 for Zn1–Zn5, IR, H NMR, C NMR, elemental
analyses, melting point, PXRD, UVꢀvis, TGA. For ESI and crystallographic data
in CIF or other electronic see DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Journal Name
3
5
36
economic benefit and waste resources. In this work, lower costs decay curve is well fitted into a double exponential function: I (t) =
Zn(II) metal salts are selected to successfully synthesize higher
A
1
exp (–t/τ
and τ
1
) + A
2
are the lifetimes for the exponential components. The
2 2
exp (–t/τ ), where I is the luminescence intensity,
synthetic yields, strong luminescence Schiff base complexes. and τ
1
Remarkably, the availability of Zn(II) complex doped with PMMA average lifetimes were calculated with Equation (1).
as a high performance luminescent materials.
2
2
τ1 A1%+ 2
τ
A2 %
A2 %
(1)
In line with the above discussion and the fact that the type of
substituents and conjugated system are the main factors to affect the
supramolecular frameworks and luminescent properties, five Schiff
τ1 A1%+ 2
τ
Quinine sulfate in 0.1 M H
2
SO
4
(quantum yield 0.546 at 350 nm)
3
7−39
1
5
was chosen as a standard.
The absolute values were calculated
base ligands, L −L , Scheme 1, carrying different substitutions and
conjugated system have been employed for the synthesis of Zn(II)
complexes. Five Zn(II) complexes, namely Zn1−Zn5, were prepared
by the reactions of corresponding ligand and ZnCl /Zn(ClO ) ,
from the fixed and known fluorescence quantum yield of the
standard reference sample through Equation (2).
2
4 2
2
I ODR
n
(2)
which display luminescence ranging from blue to yellow. The
optical properties of all the complexes were investigated by UVꢀvis
absorption and luminescence spectroscopy in solution and in the
solid state. After doping complex Zn3 with PMMA at the
concentration of 4% (Zn3ꢀPMMA), the luminescence intensities of
the polymer film material Zn3ꢀPMMA increase 19ꢀfold and its
thermal stablity temperature raised 98 ºC compared with those of
Zn3.
Q=QR
2
IR OD nR
In Equation (2), Q is the quantum yield, I is the measured integrated
emission intensity, n is the refractive index, and OD is the optical
density. The subscript R refers to the reference fluorophore of known
quantum yield. In order to minimize reꢀabsorption effects
absorbencies in the 10 mm fluorescence cuvette were kept under
0
.05 at the excitation wavelength (350 nm).
Xꢀray crystallography
Suitable crystals of complexes Zn1–Zn5 were selected and mounted
on a Rigaku R–AXIS RAPID IP diffractometer. Diffraction data
were collected using graphiteꢀmonochromatized Mo·Kα radiation (λ
4
0
=
0.71073 Å). The structures were solved with direct methods and
2
refined with full–matrix least–squares on F . All the hydrogen atoms
were constrained in geometric positions to their parent atoms and
nonꢀhydrogen atoms were refined anisotropically. The detailed
crystal structure refinement data are given in Table 1, selected bond
lengths and angles are listed in Tables S1–S2†. The CCDC numbers
are 1508968–1508972 for Zn1–Zn5, respectively.
1
5
Scheme 1. Structures of Schiff base ligands L –L .
Synthesis of the ligands and complexes
Experimental Section
1
(E)ꢀ4ꢀnitroꢀNꢀ((pyridinꢀ2ꢀyl)methylene)aniline
(L ).
2ꢀ
Materials and instrumentation
pyridinecarboxaldehyde (1.40 mL, 14.72 mmol) and 4ꢀnitroaniline
2.00 g, 14.46 mmol) were dissolved in the mixed solutions of
All reagents and solvents were purchased from commercial sources
and were used without further purification. Elemental analyses were
carried out on a Perkin–Elmer 2400 automatic analyzer. FT–IR
(
anhydrous methanol (20 mL) and tetrahydrofuran (25 mL), the
resulting mixture was heated at reflux temperature for 11 h. The
solvent was removed under reduced pressure to give yellow
powders. M.p. = 130.2–131.5 ℃ . Yield: 2.22 g (67%). Anal. Calcd
–
1
spectra data (4000–400 cm ) were collected by a Nicolet impact 410
1
FT–IR spectrometer. H NMR spectra were obtained using a Bruker
Avance–400 MHz spectrometer with Si(CH
3
)
4
as internal standard.
−
1
13
(%) for C H N O (M = 227.22 g mol ): C, 63.43; H, 3.99; N,
12 9 3 2
C NMR (150 MHz) spectra were recorded on a Bruker Avanceꢀ600
–
1
1
8.49. Found: C, 63.38; H, 3.41; N, 18.45. FTꢀIR bands (KBr, cm ):
spectrometer. Melting points were determined using a capillary
melting point apparatus and are uncorrected. Powder Xꢀray
diffraction (PXRD) patterns were recorded in the 2θ range of 5–50°
using Cu–Kα radiation by Shimadzu XRDꢀ6000 Xꢀray
Diffractometer. The thermal analyses were performed on a ZRYꢀ2P
1
ν
1
8
7
C=N 1630 (m). H NMR (400 MHz, CDCl
3
): δ 8.79 (d, J = 4.8 Hz,
H, PyꢀH
.08 (d, 2H, J = 8.8 Hz, PhꢀH3,5), 7.93 (t, 1H, J = 7.6 Hz, PyꢀH
.57 (t, 1H, J = 7.2 Hz, PyꢀH
6
), 8.61 (s, 1H, CH=N), 8.31 (d, J = 8.4 Hz, 1H, PyꢀH
3
),
),
4
5
), 6.66 (d, 2H, J = 9.2 Hz, PhꢀH2,6
): δ 163.31, 152.52, 150.26,
39.12, 137.13, 127.94, 126.39, 125.12, 121.42, 113.38 ppm.
)
13
ppm. C NMR (150 MHz, CDCl
3
thermogravimetric analysis under
a flow of air from room
1
temperature to 700 °C. A Perkin–Elmer Lambda 35 spectrometer
was used to measure the UV–vis absorption spectra of ligands and
complexes. The emission luminescence and lifetime properties were
recorded with Edinburgh FLS 920 fluorescence spectrometer.
Lifetime studies were performed using photonꢀcounting system with
a microsecond pulse lamp as the excitation source. The emission
decays were analyzed by the sum of exponential functions. The
2
(
E)ꢀ4ꢀmethylꢀNꢀ((pyridinꢀ2ꢀyl)methylene)aniline
pyridinecarboxaldehyde (1.52 mL, 15.98 mmol) and 4ꢀmethylaniline
1.77 mL, 15.88 mmol) were dissolved in 20 mL of anhydrous
(L ).
2ꢀ
(
methanol and the resulting mixture was heated at reflux temperature
for 3 h. The solvent was removed under reduced pressure and the
residue was recrystallized from the mixed solvent of nꢀhexane and
2
| J. Name., 2012, 00, 1-3
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dichloromethane to give yellow crystals. M.p. = 67.5–68.7 ℃ . Yield: = 5.2 Hz, QuinoloneꢀH
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6
), 7.70 (d, 2H, J = 5.2 Hz, PhꢀH2,6), 7.65 (d,
−
1
2
.79 g (90%). Anal. Calcd (%) for C H N (M = 196.25 g mol ): 2H, J = 4.8 Hz, PhꢀH3,5), 7.53 (d, 2H, J = 4.8 Hz, pꢀPhꢀH2,6), 7.47 (t,
13 12 2
C, 79.56; H, 6.16; N, 14.27. Found: C, 79.55; H, 6.17; N, 14.28. FTꢀ 2H, J = 5.6 Hz, pꢀPhꢀH3,5), 7.37 (t, 1H, J = 4.8 Hz, pꢀPhꢀH
4
) ppm.
): δ 160.49, 154.83, 149.82, 147.88,
), 8.65 (s, 1H, CH=N), 8.24 (d, 1H, J 140.47, 140.06, 136.85, 130.09, 129.65, 128.95, 128.87, 128.02,
8.0 Hz, PyꢀH ), 7.84 (t, J = 7.6 Hz, 1H, PyꢀH ), 7.40 (t, J = 5.6 Hz, 127.83, 127.43, 127.02, 121.089, 118.75, 115.41 ppm.
–1
1
13
IR bands (KBr, cm ): νC=N 1628 (m). H NMR (400 MHz, CDCl
δ 8.74 (d, 1H, J = 4.4 Hz, PyꢀH
3
):
C NMR (150 MHz, CDCl
3
6
=
3
4
1
1
H, PyꢀH
Hz, PhꢀH3,5), 2.41 (s, 3H, PhꢀCH
CDCl
25.01, 121.82, 121.12, 21.08 ppm.
E)ꢀ2ꢀmethoxyꢀNꢀ((6ꢀmethoxypyridinꢀ2ꢀyl)methylene)aniline (L ). A temperature and filtered. The filtrate was allowed to stand at room
5 2 2 2
), 7.00 (d, 2H, J = 8.4 Hz, PhꢀH2,6), 7.00 (d, 2H, J = 7.6 [ZnL Cl ] (Zn1). To a 5 mL methanol solution of ZnCl (13.3 mg,
1
3
3
) ppm. C NMR (150 MHz, 0.1 mmol) was slowly added a 25 mL dichloromethane solution of
1
3
): δ 159.63, 154.68, 149.63, 148.31, 136.81, 136.71, 129.87, L (22.7 mg, 0.1 mmol) under stirring. The mixture was stirred and
1
heated under reflux for 8 h. The mixture was then cooled to room
3
(
mixture of 2ꢀmethoxyaniline (1.90 g, 16.94 mmol) and 6ꢀmethoxyꢀ2ꢀ temperature in air. Yellow bulk crystals of Zn1 were obtained by
pyridinecarboxaldehyde (2.0 mL, 16.63 mmol) was refluxed in slow evaporation for 21 days. Yield: 21.1 mg (58%). Anal. Calcd
−
1
anhydrous methanol (30 mL) in the presence of a catalytic amount of (%) for [C H Cl N O Zn] (M = 726.98 g mol ): C, 39.65; H, 2.50;
12
9
2
3
2
2
formic acid for 12 h. After the reaction was over, the resulting N, 11.56. Found: C, 39.72; H, 2.61; N, 11.58. FTꢀIR bands (KBr,
–
1
1
solution was concentrated under reduced pressure (oil pump) to cm ): νC=N 1628(w), νZn–N 423(w). H NMR (400 MHz, CDCl
obtain brown yellow oil. Then the brown yellow residue was 8.83 (d, J = 4.8 Hz, 1H, PyꢀH ), 8.75 (s, 1H, CH=N), 8.37 (d, J = 8.4
recrystallized from nꢀhexane solvent to give yellow solids. M.p. = Hz, 1H, PyꢀH ), 8.09 (d, 2H, J = 8.4 Hz, PhꢀH3,5), 7.93 (t, 1H, J =
3
): δ
6
3
5
5.0–56.3 ℃ . Yield: 4.03 g (89 %). Anal. Calcd for C14
H
14
N
2
O
2
(M 7.6 Hz, PyꢀH
4
), 7.59 (t, 1H, J = 5.2 Hz, PyꢀH
5
), 6.64 (d, 2H, J = 8.8
): δ 165.62, 153.56,
−
1
13
=
242.27 g mol ): C, 69.41; H, 5.82; N, 11.56 %. Found: C, 69.17; Hz, PhꢀH2,6) ppm. C NMR (150 MHz, CDCl
3
–
1
1
H, 5.99; N, 11.38 %. FTꢀIR bands (KBr, cm ): νC=N 1632 (m). H 148.35, 137.94, 136.86, 130.26, 129.55, 127.12, 123.32, 115.85
NMR (400 MHz, CDCl ): δ 8.50 (s, 1H, CH=N), 7.85 (d, 1H, J = 7.2 ppm.
3
2
2
Hz, PyꢀH
PyꢀH ), 7.22 (t, 1H, J = 7.2 Hz, PhꢀH
), 6.83 (d, 1H, J = 8.0 Hz, PhꢀH ), 6.73 (t, 1H, J = 5.6 Hz, PhꢀH
.03 (s, 3H, PyꢀOCH ), 3.99 (s, 3H, PhꢀOCH ) ppm. C NMR (150 filtrate was allowed to stand at room temperature in air. Colorless
5
), 7.73 (t, 1H, J = 8.0 Hz, PyꢀH
), 7.09 (d, 1H, J = 7.2 Hz, Phꢀ mmol) were refluxed in 20 mL of anhydrous methanol for 4 h. The
), mixture was then cooled to room temperature and filtered. The
4 2 2
), 7.56 (d, 1H, J = 7.2 Hz, [ZnL Cl ] (Zn2). L (19.6 mg, 0.1 mmol) and ZnCl (13.6 mg, 0.1
3
4
H
6
3
5
1
3
4
3
3
MHz, CDCl
3
): δ 163.68, 152.02, 150.60, 138.99, 128.07, 126.88, bulk crystals of Zn2 were obtained by slow evaporation after 29
days. Yield: 21.7 mg (65%). Anal. Calcd (%) for C13 Zn (M
123.93, 121.86, 118.17, 116.38, 114.10, 112.78, 54.30, 53.50 ppm.
2 2
H12Cl N
−
1
N,N′ꢀbis(6ꢀmethoxyꢀ2ꢀpyridinylmethylene)phenyleneꢀ1,3ꢀ
= 332.52 g mol ): C, 46.96; H, 3.64; N, 8.42. Found: C, 47.01; H,
4
–1
dimethanamine (L ). 6ꢀmethoxyꢀ2ꢀpyridinecarboxaldehyde (1.80 3.57; N, 8.40. FTꢀIR bands (KBr, cm ): ν
1622(w), νZn–N 442(w).
C=N
1
mL, 15.00 mmol) and 1,3ꢀbenzenedimethanamine (1.00 mL, 7.50
H NMR (400 MHz, CDCl
3
): δ 8.93 (d, 1H, J = 5.6 Hz, PyꢀH
), 7.95 (t, J = 7.2 Hz,
), 7.40 (d, 2H, J = 8.0 Hz,
solvent was removed under reduced pressure and the residue was PhꢀH2 ), 7.02 (d, 2H, J = 7.6 Hz, PhꢀH3,5), 2.46 (s, 3H, PhꢀCH3)
6
), 8.75
mmol) were dissolved in 25 mL of anhydrous methanol and the (s, 1H, CH=N), 8.28 (d, 1H, J = 8.4 Hz, PyꢀH
resulting mixture was heated at reflux temperature for 4.5 h. The 1H, PyꢀH ), 7.40 (t, J = 6.8 Hz, 1H, PyꢀH
3
4
5
,6
13
froze for 2 h to give cream solids. M.p. = 74.6–75.6 ℃ . Yield: 2.25 g ppm. C NMR (150 MHz, CDCl
3
): δ 163.38, 153.72, 151.04,
−
1
(80%). Anal. Calcd (%) for C22
H N O (M = 374.44 g mol ): C, 148.54, 135.36, 133.83, 128.80, 125.49, 122.46, 119.56, 23.17 ppm.
22 4 2
3
3
70.57; H, 5.92; N, 14.96. Found: C, 70.68; H, 5.94; N, 14.88. FTꢀIR [Zn(L )
2
]·(ClO
4
)
2
(Zn3).
L
(48.3 mg, 0.2 mmol) and
–1
1
bands (KBr, cm ): ν
1651 (s). H NMR (400 MHz, CDCl ): δ Zn(ClO ) ·6H O (37.2 mg, 0.1 mmol) were refluxed in 25 mL of
C=N
3
4 2
2
8
.38 (s, 2H, CH=N), 7.32ꢀ7.65 (m, 6H, PyꢀH3,4,5), 6.76ꢀ7.27 (m, 4H, anhydrous methanol for 2 h. The mixture was then cooled to room
13
PhꢀH2,4,5,6), 4.86 (s, 4H, ꢀCH
NMR (150 MHz, CDCl ): δ 163.89, 163.04, 152.10, 139.18, 138.89, temperature in air. Yellow bulk crystals of Zn3 were obtained by
28.78, 127.93, 126.95, 114.28, 112.22, 64.91, 53.42 ppm.
2
ꢀ), 3.97 (s, 3H, PyꢀOCH
3
) ppm.
C
temperature and filtered. The filtrate was allowed to stand at room
3
1
slow evaporation for 23 days. Yield: 53.9 mg (72%). Anal. Calcd
5
−1
(E)ꢀ4ꢀphenylꢀNꢀ((quinolinꢀ2ꢀyl)methylene)aniline (L ). Quinolineꢀ2ꢀ (%) for C28
H28Cl
2
N
4
O
12Zn (M = 748.83 g mol ): C, 44.91; H, 3.77;
–
carboxaldehyde (0.83 g, 5.29 mmol) and 4ꢀphenylaniline (0.90 g, N, 7.48. Found: C, 44.88; H, 3.81; N, 7.43. FTꢀIR bands (KBr, cm
1
1
5.32 mmol) were dissolved in 35 mL of anhydrous methanol and the
3
): νC=N 1619(m), νZn–N 443(w). H NMR (400 MHz, CDCl ): δ 8.85
resulting mixture was heated at reflux temperature for 2 h. The (s, 1H, CH=N), 8.34 (d, 1H, J = 8.0 Hz, PyꢀH ), 8.09 (t, 1H, J = 8.8
5
solvent was removed under reduced pressure to give yellow solids. Hz, PyꢀH
4
), 7.78 (d, 1H, J = 8.4 Hz, PyꢀH
), 7.12 (d, 1H, J = 6.0 Hz, Phꢀ
), 4.25 (s, 3H, PyꢀOCH ), 4.18 (s,
3
), 7.51 (t, 1H, J = 8.4 Hz,
M.p. = 125.1–126.8 ℃ . Yield: 1.21 g (74%). Anal. Calcd (%) for PhꢀH ), 7.45 (d, 1H, J = 7.2 Hz, PhꢀH
4
6
−
1
C
22
H
16
N
2
(M = 308.38 g mol ): C, 85.69; H, 5.23; N, 9.08. Found:
H
3
), 7.02 (t, 1H, J = 5.6 Hz, PhꢀH
5
3
–1
13
C, 85.75; H, 5.28; N, 9.05. FTꢀIR bands (KBr, cm ): ν
1625 (w). 3H, PhꢀOCH ) ppm. C NMR (150 MHz, CDCl ): δ 164.51, 153.47,
C=N
3
3
1
H NMR (400 MHz, CDCl
.6 Hz, QuinoloneꢀH ), 8.31 (d, 1H, J = 5.6 Hz, QuinoloneꢀH
d, 1H, J = 6.0 Hz, QuinoloneꢀH
3
): δ 8.91 (s, 1H, CH=N), 8.43 (d, 1H, J = 150.45, 138.56, 128.74, 127.63, 125.44, 122.05, 121.76, 119.25,
5
3
5
), 8.22 117.84, 112.47, 55.82, 54.07 ppm.
4
4
(
2 2 4 2
), 8.06 (d, 1H, J = 6.0 Hz, [Zn L Cl ] (Zn4). L (37.5 mg, 0.1 mmol) and ZnCl (37.2 mg, 0.2
QuinoloneꢀH ), 7.94 (t, 1H, J = 5.6 Hz, QuinoloneꢀH ), 7.80 (t, 1H, J mmol) were refluxed in 25 mL of anhydrous acetonitrile for 2 h. The
8
7
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mixture was then cooled to room temperature and filtered. The
The infrared spectra of these five Zn(II) complexes (see Fig.s
filtrate was allowed to stand at room temperature in air. Colorless S1–S5†) are similar to that of the corresponding ligand and the IR
bulk crystals of Zn4 were obtained by slow evaporation for 6 days. assignments of selected diagnostic bands are given in the
1
5
4 2 2 2
Yield: 43.5 mg (67%). Anal. Calcd (%) for C22H22Cl N O Zn (M = experimental section. In the IR spectra of ligands L –L , the
−
1
6
47.02 g mol ): C, 40.84; H, 3.43; N, 8.66. Found: C, 40.85; H, existence of C=N bonds is clearly demonstrated by the presence of
–
1
–1
3
1
.47; N, 8.59. FTꢀIR bands (KBr, cm ): ν
1639(m), νZn–N 428(w). strong characteristic C=N peaks in a range of 1628–1651 cm .
C=N
–1
H NMR (400 MHz, CDCl
3
): δ 8.42 (s, 2H, CH=N), 7.70ꢀ8.07 (m, These bands undergo negative shifts of 2–13 cm in the complexes,
6
4
1
1
H, PyꢀH3,4,5), 6.97ꢀ7.52 (m, 4H, PhꢀH2,4,5,6), 5.10 (s, 4H, ꢀCH
2
ꢀ), which may be attributed to the coordination of the nitrogen atom of
1
3
41,42
.04 (s, 3H, PyꢀOCH
3
) ppm. C NMR (150 MHz, CDCl
3
): δ 163.97, the imine to the metal ion.
This is further confirmed by the
–1
62.10, 150.72, 140.19, 134.47, 129.31, 128.93, 126.41, 116.52, presence of a ν(M–N) vibration in the region 423–443 cm in all the
43
1
1
5
15.54, 63.75, 54.48 ppm.
complexes. The H NMR spectra of the ligands L –L and its
5
5
[
ZnL Cl
2
] (Zn5). L (31.0 mg, 0.1 mmol) and ZnCl
2
(13.6 mg, 0.1 Zn(II) complexes were recorded in CDCl
3
at room temperature (see
1
mmol) were refluxed in 25 mL of anhydrous acetonitrile for 2 h. The Fig.s S6–S10†). In the H NMR spectra, the chemical shift values of
mixture was then cooled to room temperature and filtered. The the protons in the complexes are slightly different from those
filtrate was allowed to stand at room temperature in air. Yellow bulk observed for the nonꢀcoordinated ligand. Of particular note is the
crystals of Zn5 were obtained by slow evaporation for 3 days. Yield: HC=N resonances of the complexes Zn1–Zn5, which are moved
2
6.3 mg (59%). Anal. Calcd (%) for C22
H
16Cl
2
N
2
Zn (M = 444.64 g downfield due to coordination between the imine nitrogen and the
−
1
44
mol ): C, 59.43; H, 3.63; N, 6.30. Found: C, 59.37; H, 3.66; N, Zn(II) center. For the complexes, the imine proton is moved
–
1
1
13
6
.25. FTꢀIR bands (KBr, cm ): νC=N 1621(w), νZn–N 428(w).
H
downfield at most 0.04 ppm. In the C NMR spectra (see Fig.s S11–
): δ 9.01 (s, 1H, CH=N), 8.73 (d, 1H, J = 8.8 S15†), the signals of the C=N nuclei are observed at δ 159.63–
), 8.47 (d, 165.62 ppm.
H, J = 7.6 Hz, QuinoloneꢀH ), 8.10 (d, 1H, J = 5.6 Hz, Quinoloneꢀ We performed powder Xꢀray diffraction patterns on complexes
), 7.97 (t, 1H, J = 8.8 Hz, Zn1–Zn5 to check the purity of the bulk products. From Fig S16†,
), 7.87 (d, 2H, J = 8.0 Hz, PhꢀH2,6), 7.77 (d, 2H, J = we can see that all major peak positions of the measured patterns are
.4 Hz, PhꢀH3,5), 7.64 (d, 2H, J = 7.2 Hz, pꢀPhꢀH2,6), 7.52 (t, 2H, J = in good agreement with those simulated. Furthermore, the
NMR (400 MHz, CDCl
3
3 5
Hz, QuinoloneꢀH ), 8.67 (d, 1H, J = 8.4 Hz, QuinoloneꢀH
1
2
H
8 7
), 8.04 (t, 1H, J = 7.6 Hz, QuinoloneꢀH
QuinoloneꢀH
6
8
8
13
.8 Hz, pꢀPhꢀH3,5), 7.45 (t, 1H, J = 6.4 Hz, pꢀPhꢀH ) ppm. C NMR differences in intensity may be due to the preferred orientation of the
4
(
150 MHz, CDCl
3
): δ 161.45, 150.59, 147.90, 145.11, 139.79, crystal products. To further understand the structures of these
1
1
39.14, 133.69, 130.16, 129.99, 129.17, 128.58, 127.15, 127.04, complexes, single crystals were obtained and analyzed by Single
26.64, 126.49, 124.12, 117.06, 115.76 ppm.
Crystal Xꢀray Diffraction. The crystallographic data for these
complexes Zn1–Zn5 are listed in Table 1.
Fabrication of complex Zn3–PMMA films
Description of the structures
PMMA was doped with complex Zn3 in proportions of 0.25%,
1
0.5%, 0.75%, 1.0%, 2.0%, 4.0% and 6.0%. The PMMA powder was
[
ZnL Cl
2
] (Zn1). Complex Zn1 crystallized in the monoclinic space
dissolved in N,N′–dimethylformamide (DMF), followed by addition group P2 /c. As shown in Fig. 1a, the asymmetric unit of Zn1
1
1
of the required of complex Zn3 in DMF solution and the resulting consists of one Zn(II) atom, one L ligand and two chlorine anions.
mixture was heated at 50 ºC for 60 min. The polymer film was Using Addison’s model,45,46 the coordination geometry around the
obtained after the total evaporation of excess solvent at 60 ºC zinc atom in Zn1 (τ
4
= 0.772) can be better described as a
according to the literatures.
tetrahedron. It is noteworthy that it gives rise to a fiveꢀmembered
ring after coordinated, which have coplanar with inherency of
pyridyl ring and indirectly results the extended conjugate. In
complex Zn1, the pyridine ring and the phenyl rings of L ligand are
Results and Discussion
1
Synthesis and spectral characterization
twisty and the dihedral angle is ~ 29.301°. The average bond lengths
1
5
The structures of five Schiff base ligands (L –L ) are shown in of Zn–N and Zn–Cl are 2.145(2) and 2.281(7) Å, respectively. The
Scheme 1. Yields for these ligands varied from 67 to 90%. Using a bond angles around the Zn(II) ion are in the range of 77.84(6)–
selfassembled method, these ligands were reacted with 132.87(5)°. The selected bond lengths and bond angles of complex
2 4 2
ZnCl /Zn(ClO )
to obtain a series of complexes, namely, Zn1–Zn5. Zn1 are given in Table S1†. Single crystal analysis shows that
complex Zn1 is constructed by the C–H···O and C–H···Cl hydrogen
bonds interactions and π···π stacking interactions to aggregate in a
threeꢀdimensional supramolecular network (Fig. 1b). The
Xꢀray quality single crystals of five Zn(II) complexes were grown
from slow evaporation of solutions and readily obtained in good
yields within the range of 58−72%. The details of the synthesis are
given in the experimental section. Some important analytical and
physical data are listed in Table S3†. The composition of the ligands
and complexes were calculated and compared with the experimental
values. We confirm that all the complexes are stable in the solid state
under exposure to air. The complexes are soluble in common organic
solvents, such as chloroform, dimethylsulfoxide and acetonitrile.
4
7
π
phenyl···πphenyl and πphenyl···πpyridyl distances are 3.561 and 3.802 Å,
respectively. The detailed data of C–H···O/Cl hydrogen bonds and
π···π interactions for Zn1 are listed in Table 2. If the mononuclear
unit is viewed as the nodes, the C–H···O/Cl and π···π interactions
as the linkers, the resulting threeꢀdimensional supramolecular
structure may be simplified as a pcu net with the point symbol of
1
2
3
{
4 ·6 },
as
depicted
in
Fig.
1c.
4
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Table 1. Crystallographic and structural determination data for complexes Zn1–Zn5.
Zn1
1508968
Zn2
1508969
Zn3
1508970
Zn4
1508971
Zn5
1508972
CCDC No.
formula
Mr
cryst syst
space group
[C12
H
9
Cl
726.98
Monoclinic
P2 /c
2
N
3
O
2
Zn]
2
C
13
H
12Cl
2
N
2
Zn
C
28
H
28Cl
2
N
4
O
12Zn
C
22
H
22Cl
4
N
2
O
2
Zn
2
22 2 2
C H16Cl N Zn
444.64
332.52
Monoclinic
P2 /c
748.83
Triclinic
647.02
Triclinic
P2
Triclinic
_
_
1
1
1
/c
P1
P1
a [Å]
b [Å]
c [Å]
α [˚]
β [˚]
γ [˚]
9.401(19)
7.409(15)
20.197(4)
90
98.51(3)
90
1391.3(5)
2
1.735
11.952(7)
9.847(8)
14.876(6)
90
127.535(19)
90
1388.33(15)
4
1.591
8.441(5)
10.097(8)
15.062(2)
8.473(5)
9.740(5)
12.753(19)
15.887(2)
90
118.539(11)
90
2680.9(6)
4
1.603
19.157(13)
103.765(2)
94.754(2)
101.537(2)
1539.29(18)
2
12.535(6)
82.088(4)
72.926(5)
78.764(5)
966.44(9)
2
3
Volume [Å ]
Z
–
3
D
c
[g·cm
]
1.616
1.043
1.528
1.556
–
1
ꢁ
[mm
]
2.152
2.136
2.215
F (000)
728
672
768
1304
452
Θ range [˚]
h range
k range
l range
data/restraints/params
3.21 – 27.45
3.43 – 27.48
–15 ≤ h ≤ 15
–12 ≤ k ≤ 12
–17 ≤ l ≤ 19
3160 / 0 / 163
1.065
0.0635, 0.1528
0.1134, 0.1771
1.383, –0.492
3.01 – 25.00
3.02 – 25.36
3.03 – 25.00
–10 ≤ h ≤ 10
–11 ≤ k ≤ 11
–14 ≤ l ≤ 11
3398 / 0 / 244
0.917
0.0505, 0.0775
0.0884, 0.0882
0.361, –0.496
–11 ≤ h ≤ 12
–9 ≤ k ≤ 9
–26 ≤ l ≤ 26
3176 / 0 / 181
1.017
0.0283, 0.0662
0.0360, 0.0688
0.319, –0.300
–10 ≤ h ≤ 10
–12 ≤ k ≤ 11
–22 ≤ l ≤ 22
5330 / 0 / 424
1.073
0.0731, 0.1935
0.1175, 0.2164
1.748, –0.700
–17 ≤ h ≤ 17
–15 ≤ k ≤ 15
–17 ≤ l ≤ 19
4857 / 0 / 307
0.795
0.0480, 0.1166
0.1450, 0.1692
0.495, –0.306
GOF
a
R
R
1
, wR
, wR
2
[I>2σ(I)]
[all data]
a
1
2
–3
ꢁρmax, ꢁρmin [e·Å ]
a
2
2
2
2 2 1/2
1 o c o 2 o c o
R = ∑||F | – |F ||/∑|F |; wR = [∑[w (F – F ) ]/∑[ w (F ) ]] .
Fig. 1 (a) Crystal structure of Zn1. Thermal ellipsoid is drawn at 50% probability. H atoms have been omitted for clarity. (b) The 3D network structure in Zn1. (c) The
1
2
3
3
D sixꢀconnected network with pcu topology and point symbol {4 ·6 } of Zn1. Dotted lines represent the C–H···O and C–H···Cl interactions.
2
[
ZnL Cl
2
] (Zn2). Crystal refinement data of complex Zn2 implied distance of H3A···Cl1 is 2.929 Å, and the C3–H3A···Cl2 angle is
/c space group. As shown 161.099°) to generate a oneꢀdimensional chain (Fig. 2a). In addition,
that it belongs to a monoclinic system, P2
1
in Fig. S17a†, the Zn(II) center adopts a distorted tetrahedral the molecules are also interconnected by C5–H5A···Cl2, C6–
geometry (τ = 0.888) coordinated by two nitrogen atoms of (E)ꢀ4ꢀ H6A···Cl1 and C8–H8A···Cl2 hydrogen bonds interactions (the
4
2
methylꢀNꢀ((pyridinꢀ2ꢀyl)methylene)aniline (L ) and two terminal distances of H5A···Cl2, H6A···Cl1 and H8A···Cl2 are 2.860, 2.895
chlorine ions (Zn1–N1 = 2.054(5) Å, Zn1–N2 = 2.092(5) Å, Zn1– and 2.945 Å, respectively) to aggregate in a twoꢀdimensional layer
Cl1 = 2.203(2) Å, Zn1–Cl2 = 2.194(2) Å). The bond angles for (Fig. 2b), and the π···π stacking interactions with centroid···centroid
Zn(II) are in the range of 80.6(2)–125.0(4)°. The dihedral angle distances of 3.662 and 3.872 Å exist in the sheet (Fig. S17b†). These
between the pyridyl ring and the phenyl ring is 7.177° (Table 2), 1D and 2D structures are both constructed to the resulting 3D
which is close to parallel. In the bc plane, the independent units are supramolecular
linked through C3–H3A···Cl1 hydrogen bonds interactions (the
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structure of Zn2 (Fig. 2c). Topology analysis shows that the overall interactions (C7–H7D···O6 and C13–H13A···O11) based on the O
−
network of Zn2 features a 3D pcu topology with a point symbol of atom of ClO
{
4
anion are found (Fig. 3d). Besides these, the
1
2
3
4 ·6 } by denoting the mononuclear unit as 6ꢀconnected nodes and intermolecular hydrogen bonds interactions play important roles in
the C–H···Cl interactions as linkers, respectively.
forming the higher dimensional structure. As shown in Fig. 3d, the
adjacent molecules are linked by C7–H7B···O5, C7–H7C···O8,
C11–H11B···O12 and C28–H28B···O11 hydrogen bonds
interactions to form a 3D supramolecular structure. The distances of
H7B···O5, H7C···O8, H11B···O12 and H28B···O11 are 2.543,
2
.570, 2.698 and 2.358 Å, respectively. Finally, the overall topology
12
3
of Zn3 can also be defined as the {4 ·6 } topology as illustrated in
Fig. 3e.
4
[
Zn
2
L Cl
4
] (Zn4). The asymmetric unit of complex Zn4 consists of
2
+
4
two crystallographically independent Zn cations, one ligand L ,
and four Cl anions (Fig. 4a). The lengths and angles of center ion
−
coordination bond (see Table S2†) have small differences. In
complex Zn4, the zinc(II) ions are fourꢀcoordinated, and the
2
+
coordination geometry of Zn are distorted tetrahedron (Fig. 4b),
with geometry index τ4 = 0.883 (Zn1) and 0.863 (Zn2). In the
binuclear structure unit, intermetallic Zn(1)···Zn(2) distance is
Fig. 2 (a) The 1D chain structure in Zn2. (b) The 2D layer structure in Zn2. (c)
1
2
3
The 3D sixꢀconnected network with pcu topology and point symbol {4 ·6 } of
Zn2. Dotted lines represent the C–H···Cl interactions.
8
.362(11) Å. Due to the flexibility of –CH – group, the pyridyl and
2
4
3
phenyl rings of the L ligand in Zn4 are arranged in a nearly
perpendicular fashion (77.840°/80.059°). The adjacent binuclear
molecules are interconnected through C6–H6A···Cl4, C7–
H7B···Cl4, C10–H10A···Cl3, and C13–H13A···Cl1 hydrogen
bonds interactions to form a 3D supramolecular structure (Fig. 4c).
The H6A···Cl4, H7B···Cl4, H10A···Cl3, and H13A···Cl1 distances
are 2.626, 2.813, 2.922 and 2.612 Å, respectively. From the
topological point of view, the binuclear unit could be considered as
the node, and hydrogen bonds C–H···Cl could be considered as the
linkers. Thus, the threeꢀdimensional net of Zn4 can be described as a
[
Zn(L )
2
]·(ClO
4
)
2
(Zn3). The asymmetric unit of complex Zn3
2
+
3
consists of one crystallographically independent Zn cation, two L
−
2+
ligands, and two ClO
coordinated with slightly distorted octahedral coordination geometry
ZnN ] containing four N atoms (N1, N2, N3 and N4) and two O
4
anions (Fig. 3a). Every Zn cation is sixꢀ
[
4 2
O
3
atoms (O2 and O4) from L (Fig. 3b). The bond angles around the
Zn(II) ion are in the range of 70.3(2)–152.17(19) Å. The selected
bond distances and angles are shown in Table S2†. In complex Zn3,
the dihedral angles (88.765°) between two
approximately perpendicular (Fig. 3c). In the molecular packing
structure of complex Zn3, the intramolecular hydrogen bonds
3
L
ligands is
1
7
4
7ꢀconnected with the point symbol of {4 ·6 } (Fig. 4d).
Fig. 3 (a) Crystal structure of Zn3. Thermal ellipsoid is drawn at 50% probability. H atoms have been omitted for clarity. (b) Coordination geometry of zinc(II) ions. (c)
3
Depiction of the dihedral angle between two L ligands. (d) The 3D network structure in Zn3. (e) The 3D sixꢀconnected network with pcu topology and point symbol
1
2
3
{
4 ·6 } of Zn3. Dotted lines represent the C–H···O interactions.
6
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distances and angles are listed in Table S2†. In complex Zn5, the
independent units are linked through hydrogen bonds C10–
H10A···Cl2 of 2.851 Å, C12–H12A···Cl2 of 2.872 Å and C18–
H18A···Cl1 of 2.947 Å interactions respectively, to generate a oneꢀ
dimensional “waveꢀlike” chains (Fig. 5b). Significantly, additional
intermolecular π···π interactions with separations of about 3.657 Å
(
Fig. 5b) also provide further stabilization in the complex Zn5. The
detailed data of the noncovalent bond interactions (C–H···O/Cl and
π···π) for all complexes are listed in Table 2.
Fig. 4 (a) Crystal structure of Zn4. Thermal ellipsoid is drawn at 50% probability.
H atoms have been omitted for clarity. (b) Coordination geometry of zinc(II) ions.
(
c) The 3D network structure in Zn4. (d) The 3D sevenꢀconnected network and
17
4
point symbol {4 ·6 } of Zn4. Dotted lines represent the C–H···Cl interactions.
5
[
ZnL Cl
2
] (Zn5). The singleꢀcrystal Xꢀray diffraction analysis
_
at complex Zn5 crystallizes in the triclinic system, space
reveals th
group P1 with one molecule of the complex in the unit cell. As
shown in Fig. 5a, the coordination number of Zn(II) is four (τ
4
=
5
0
.888) with two nitrogen atoms from ligand L and two terminal
chlorine atoms. Complex Zn5 has the dihedral angles of 10.161°,
between quinoline ring and phenyl ring, which indicate that Zn5
displays better coplanarity. The distances of Zn1–N1 and Zn1–N2
are 2.070(3) Å and 2.093(3) Å, in agreement with the values of a
Fig. 5 (a) Crystal structure of Zn5. Thermal ellipsoid is drawn at 50% probability.
H atoms have been omitted for clarity. (b) The 1D “waveꢀlike” chain structure in
Zn5. Dotted lines represent the C–H···Cl and π···π interactions.
48
similar zinc complex. The distance of Zn1–Cl2 (2.215(12) Å) is
longer than that of Zn1–Cl1 (2.177(11) Å). The detailed bond
Table 2. Structural and geometrical parameters for complexes Zn1–Zn5.
a
Complex
Addison parameter (τ
4
)
Dihedral angle (deg)
29.301
D–H···A
C4–H4A···O2
C6–H6A···Cl1
D–H (Å)
0.930
H···A (Å)
2.608
D···A (Å)
3.291
D–H···A (deg)
130.684(1)
Dimension
3D
0
.772
.888
—
Zn1
0.930
2.854
3.777
3.663
3.561
3.802
3.840
3.554
3.610
3.614
3.662, 3.872
3.442
3.489
3.495
3.416
3.550
3.326
3.715
3.527
3.739
3.569
3.534
3.607
3.754
3.861
171.515(9)
C9–H9A···Cl1
0.930
2.936
136.002(1)
c
π
π
Cg1···πCg1
Cg1···πCg2
d
0
7.177
C3–H3A···Cl1
C5–H5A···Cl2
C6–H6A···Cl1
C8–H8A···Cl2
0.950
0.950
0.950
0.950
2.929
2.860
2.895
2.945
161.099(3)
133.958
3D
3D
Zn2
Zn3
132.987(3)
128.480(4)
π
Cg1···πCg2
20.087, 1.924
C7–H7B···O5
0.980
0.980
0.980
0.950
0.950
0.980
2.543
2.570
2.692
2.698
2.600
2.358
152.544(5)
156.181(5)
139.420(5)
132.923(6)
178.479(6)
169.181(5)
C7–H7C···O8
C7–H7D···O6
C11–H11B···O12
C13–H13A···O11
C28–H28B···O11
π
Cg1···πCg2
0
.883, 0.863
77.840, 80.059
C6–H6A···Cl4
0.930
0.960
0.930
0.930
0.930
0.930
0.930
2.626
2.813
2.922
2.612
2.851
2.872
2.947
163.285(7)
16.261(1)
3D
1D
Zn4
Zn5
C7–H7B···Cl4
C10–H10A···Cl3
C13–H13A···Cl1
C10–H10A···Cl2
C12–H12A···Cl2
127.918(1)
171.299(7)
139.221(5)
158.769(7)
167.708(8)
b
0
.888
10.161
C18–H18A···Cl1
e
π
Cg2···πCg3
3.657
a
b
c
d
e
Between the pyridyl ring and phenyl ring; Between the quinoline ring and phenyl ring;
Cg1 = phenyl ring;
Cg2 = pyridyl ring;
Cg3 = quinoline ring.
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Photophysical Studies. Absorption Properties of the Zinc(II) polar nature in the solidꢀstate environment (in addition to the specific
Complexes in CH
CN. The UV−vis absorption spectra of the ligands interactions at the solid state). We also drawn the corresponding
L –L and complexes Zn1–Zn5 were recorded at room temperature emission energy spectra of the ligands and complexes (Fig. S20†)
3
1
5
−
1
3
in CH CN (10 ꢁmol L ). Fig. 6 shows the absorption spectra of and summarized the emission energy data in the Table S4†. In
complexes Zn1–Zn5 in acetonitrile. It is found that all the acetonitrile solution, the maxima emission energies shift 0.08−0.57
complexes exhibit two distinct absorption bands at ca. 280 nm and eV compared with those in the solid state. Among the complexes,
ca. 350 nm. The numerical values of the maximum absorption Zn2 shows the largest shift (0.42 eV). Meanwhile, the full width at
wavelength and molar extinction coefficients (ε) are listed in Table halfꢀmaximum (FWHM) of the emission band decreases from
3
. For complexes Zn1–Zn5, these absorption bands are similar to acetonitrile solution to the solid state (Table 3). All luminescence
the corresponding ligands (Fig. S18†) which can be assigned to the quantum yields of complexes Zn1–Zn5 in solution were measured
4
9
58
π–π* transitions of the ligands. The low energy absorption bands of by the optical dilute method of Demas and Crosby with a standard
complexes Zn2–Zn5 were 341, 375, 340, 374 nm, respectively, of quinine sulfate (Φ = 0.546) and are listed in Table 3. The
r
which shifted to longer wavelengths compared to that of Zn1 (330 luminescence quantum yield of Zn1–Zn5 in CH CN is 0.015, 0.106,
3
nm) due to the increase of electronꢀdonating groups and conjugated 0.533, 0.149 and 0.228, respectively, which is higher than that of the
system.
corresponding ligand. Particularly, the quantum yields of Zn3 (Φ =
F
3
0
.533) is ca. 11ꢀfold to L (Φ = 0.048). This is because the ligands
F
coordinated with zinc(II) ions increase the rigidity of the molecular
edifice and reduce the loss of energy by radiationless thermal
5
9
vibrations.
1
5
The luminescence decay profiles of ligands L –L and the
corresponding zinc(II) complexes were measured at their optimal
excitation wavelengths in the solid state and acetonitrile solution at
2
98 K. The detailed data are listed in Table S5†. A general trend is
that the luminescence lifetimes for complexes Zn1–Zn5 either in the
solid state or acetonitrile solution at 298 K is longer than that of the
1
5
corresponding ligands L –L . The most obvious observation is that
the lifetime of Zn1 (τ = 7.60 ꢂs) is 1.6ꢀfold to the corresponding
1
3
Fig. 6 UV−vis absorption spectra of Zn1–Zn5 in CH CN at room temperature.
ligand L (τ = 4.75 ꢂs) in acetonitrile solution. This is attributed to
6
0
the more stable structure and interaction upon coordination.
SolidꢀState and Solution Luminescence Properties of the Zinc(II)
Meanwhile, the luminescence lifetimes of the ligand and
1
0
Complexes. Luminescent zinc(II) complexes possessing closed d
shells are superior potential candidates as valuable luminescent
corresponding complexes in the solid state (τ = 7.71–13.06 ꢂs for
1
5
L –L ; τ = 7.90–14.58 ꢂs for Zn1–Zn5) are longer than those in
5
0–52
1
5
materials;
thus, we probed the luminescence properties of Zn1–
acetonitrile solution (τ = 4.75–7.48 ꢂs for L –L ; τ = 7.60–8.78 ꢂs
for Zn1–Zn5), which might be attributed to their less polar nature in
Zn5 in the solid state and acetonitrile solution at room temperature.
6
1
Selected data are summarized in Table 3. In the solid state, the free
the solidꢀstate environment.
1
5
ligands L –L exhibit emission bands from blue to green centered at
4
46, 474, 521, 472, and 531 nm (Fig. S19a† and S19b†),
5
3,54
respectively, which may be attributed to the π*–π transitions.
For
the complexes Zn1–Zn5, the emission bands are observed at 461,
83, 532, 514, and 592 nm (Fig. 7a and 7b), respectively. Due to the
4
similarity of the emission bands with that of the corresponding
ligand, the emissions of these zinc(II) complexes may be attributed
55,56
to the intraligand transitions.
In addition, the emission bands of
Zn1–Zn5 occur redꢀshifted compared to that of the corresponding
ligand, which may be attributed to the coordination of ligand to the
metal centers. A trend is observed in λem with Zn1 < Zn2 < Zn4 <
Zn3 < Zn5 which is consistent with the electronꢀdonating ability (–
NO
2 3 3
< –CH < –OCH ) of substituents and conjugated system of
1
5
these ligands L –L . Electronꢀdonating effect descended the energy
difference between HOMO and LUMO, leading to λem red shifted.
In acetonitrile solution, the emission bands are observed at
5
7
1
5
3
90−465 nm and 415−560 nm for ligands L –L (Fig. S19c† and
S19d†) and complexes Zn1–Zn5 (Fig. 7c and 7d), respectively. The
Commission Internationale d’Eclairage (CIE) coordinates are
summarized in Table 3. In acetonitrile solution, the maxima
emission peaks are blueꢀshifted 18−100 nm compared with those in
the solid state. These phenomena can be explained due to the less
Fig. 7 (a) Emission spectra of Zn1–Zn5 in the solid state and (b) CIE chromaticity
diagram (1931 CIE standard). (c) Emission spectra of Zn1–Zn5 in acetonitrile
solution and (d) CIE chromaticity diagram.
8
| J. Name., 2012, 00, 1-3
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1
5
Table 3. Photophysical properties of the ligands L –L and complexes Zn1–Zn5.
a
Complex
absorption
photoluminescence in acetonitrile
photoluminescence in the solid state
–
1
–1
b
PL
λ
abs/nm (ε/M cm
)
λ
em/nm
FWHM/nm
τ/ꢁs
Ф
CIE (x, y)
λ
em/nm
FWHM/nm
τ/ꢁs
CIE (x, y)
1
L
275 (16172), 320 (20061)
285 (33040), 330 (30370)
283 (26774), 323 (21417)
295 (30540), 341 (35185)
308 (34392), 354 (20004)
261 (15695), 375 (50244)
271 (21679), 325 (29229)
267 (25871), 340 (42044)
265 (36606), 346 (27063)
261 (53841), 374 (35464)
390
430
410
415
421
514
430
460
465
560
97.05
86.51
84.18
45.81
102.45
134.77
64.37
53.06
73.28
135.94
4.75
7.60
5.58
7.95
5.22
8.78
7.48
8.02
6.67
8.50
0.009
0.015
0.017
0.106
0.048
0.533
0.037
0.149
0.055
0.228
0.16, 0.17
0.22, 0.20
0.16, 0.07
0.20, 0.18
0.23, 0.21
0.29, 0.42
0.18, 0.14
0.17, 0.19
0.22, 0.20
0.43, 0.51
−5
446
461
474
483
521
532
472
514
531
592
151.28
69.15
7.80
7.90
7.71
9.41
13.06
14.58
7.98
10.06
8.03
9.38
0.21, 0.22
0.16, 0.15
0.18, 0.24
0.21, 0.36
0.30, 0.39
0.35, 0.54
0.16, 0.26
0.30, 0.59
0.38, 0.56
0.54, 0.46
Zn1
2
L
101.71
92.97
Zn2
3
L
188.23
111.02
101.84
76.12
Zn3
4
L
Zn4
5
L
100.90
163.72
Zn5
a
−5
b
3 3
Measured in CH CN solutions (~1 × 10 M). Take quinine sulfate in CH CN as reference (~1 × 10 M, ΦPL = 0.546).
Properties of PMMA polymer films doped with complex Zn3.
Based on the nakedꢀeye visible bright luminescence of complex Zn3
(
Fig. 8a), considering the good performance of PMMA as one of the
most popular polymer matrices with low cost, easy preparation, and
good mechanical properties, a new PMMAꢀsupported hybrid film
material is constructed by doping complex Zn3 into PMMA
polymer.
To better illustrate the intra structure of PMMAꢀsupported film,
FTꢀIR spectra of pure PMMA, complex Zn3, Zn3ꢀPMMA are
–1
recorded, as shown in Fig. S21†. The band at 1732 cm for pure
PMMA is ascribed to the C=O vibrating absorption of PMMA, but
when doped with complex Zn3, the band of C=O vibrating
–
1
absorption shifts to 1726 cm . This implies that there exist
62
intermolecular interaction between complex Zn3 and PMMA.
As an extension of this work, we study the luminescence
properties of the newly designed hybrid film material. The emission
spectra of the PMMA polymer films doped with complex Zn3 at
different concentrations [0.25%, 0.5%, 0.75%, 1.0%, 2.0%, 4.0%
and 6.0% (w/w)] are similar with maximum excitation peak at 365
the Zn3ꢀPMMA films is essentially improved by doping with
complex Zn3.
Fig. 8 (a) Emission spectrum and photo of complex Zn3 under UV light with 365
nm in the solid state. (b) Emission spectra of Zn3ꢀPMMA films doped with
nm (Fig. 8b). The emission bands are assigned to the π*–π
0
.25%–6% of Zn3. (c) Emission spectrum and photo of Zn3ꢀPMMA at 4%
3
transitions of ligand L . Noticeably, the luminescence intensity of concentration under UV light with 365 nm. (d) Comparison of the intensity and
the maximum emission increases with the increasing concentration integrated intensity of Zn3ꢀPMMA films doped with 0–6% of Zn3.
of complex Zn3 from 0.25% to 4.0%, and begin to decreases when
doping concentration surpasses 4.0%. It can be attributed to the fact
Conclusions
that with a low concentration of complex Zn3 in the PMMA
polymer, the complex Zn3 can disperse uniformly in the PMMA
In summary, five Zn(II) complexes with different conjugated system
matrix and the PMMA effectively enhance the luminescence
were synthesized. Based on these five complexes different
behavior of the complex Zn3. Upon further increasing concentration supramolecular structures were constructed via different
of complex Zn3 after 4.0%, some aggregates formed in the film and intermolecular weaker interactions such as hydrogen bonding
the transparency of films declines, influencing the absorption of C−H···O/Cl and π···π packing interactions, which are a threeꢀ
12
3
light, resulting in intensity decrease of luminescence, which means dimensional {4 ·6 } topology for Zn1–Zn3, a threeꢀdimensional
17
4
luminescence quenching of complex Zn3. Comparing the emission {4 ·6 } topology for Zn4, and a oneꢀdimensional “waveꢀlike”
spectra of Zn3 (Fig. 8a) and Zn3ꢀPMMA (Fig. 8c), the chains for Zn5. The emission maximum wavelengths of complexes
Zn1–Zn5 can be tuned in a large range of 461–592 nm due to the
electron donating ability and conjugated system of the ligands. After
doping complex Zn3 with PMMA matrix, PMMAꢀsupported doped
polymer film materials was obtained, which displays excellent green
luminescent properties with enhanced luminescent intensities and
thermal stability. Thus the asꢀprepared Zn(II) complexes can be used
in the pursuit of application in farm plasticꢀfilm with optical transfer
function.
luminescence intensity and integrated intensity of Zn3ꢀPMMA is
much higher than Zn3 (Fig. 8d). Furthermore, the luminescence
intensity of the PMMA polymer film with best doping concentration
at 4.0% reached 19 times of complex Zn3. TG analysis of Zn3ꢀ
PMMA films shows no weightꢀloss in the temperature range of 25–
2
78 ºC (Fig. S22†), revealing a significant increase of 98 ºC in
comparison with Zn3, which suggests that the thermal stability of
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Journal Name
Sivakumar, A. A. Khandari and A. Frontera, CrystEngComm,
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Acknowledgements
2
2
This work was supported by National Natural Science
Foundation of China (Grant 21371040 and 21571042), the
National Key Basic Research Program of China (973 Program,
No. 2013CB632900).
2
714–2721.
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Different Conjugated System Zn(II) Schiff Base Complexes:
Supramolecular Structure, Luminescent Properties and Application
in PMMA-Doped Hybrid Material
Yu-Wei Dong, Rui-Qing Fan,* Wei Chen, Hui-Jie Zhang, Yang Song, Xi Du, Ping
Wang, Li-Guo Wei, and Yu-Lin Yang,*
Supramolecular structures and luminescent properties of Zn(II) Schiff base complexes
based on the different conjugated system have been studied in detail. Complex Zn3 is
incorporated into PMMA representing high performance materials.