CN104086575B - Two (pyridine)-(4-HBA)-chloro-zinc (II) title complex and preparation method thereof - Google Patents
Two (pyridine)-(4-HBA)-chloro-zinc (II) title complex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of two (pyridine)-(4-HBA)-chloro-zinc (II) title complex, the chemical formula of this title complex is [Zn (L
1)
2l
2cl]
n, wherein L
1for pyridine, L
2for 4-HBA, adopt solution crystal process, by ZnCl
2, pyridine and 4-HBA add in methanol solution for 1:2:1 ~ 1:4:1, with ZnCl in molar ratio
2for benchmark, every 1mmol? ZnCl
2the volume needing methanol solution is 3.8 ~ 4.2mL, and at room temperature slow evaporation after stirring and dissolving, obtains colorless plate N-type waferN, separated by this monocrystalline after 14 ~ 16 days, successively through washing, drying treatment, obtains target product.The advantages such as this title complex has good stability, and synthesis is simple, easy to operate, and the high and reproducibility of productive rate is good.The crystalline material obtained is expected to obtain further research and development application in field of light emitting materials.
Description
Technical field
The present invention is specifically related to d
10two (pyridine)-(4-HBA)-chloro-zinc (II) title complex of one of metal complexes field of light emitting materials and preparation method thereof.
Background technology
In recent years, a metal-organic complex just developing rapidly as a kind of novel functional materials and become materials chemistry and other related disciplines study hotspot.The coordination compound especially with novel structure is the hot subject of inorganic chemistry worker research always, and this compounds not only has novel topological framework, and also shows some characteristics and potential application in some field.People achieve certain achievement from ligand design to structure crystalline structure, especially use pyridine, imidazoles, triazole, and the title complex that hydroxy-benzoic acid class part and various derivative thereof and metal ion reaction designing synthesize is of a great variety, and configuration is various.This kind of part contains conjugated pi in molecule is good for, and has electron transmission and transmission ofenergy performance in good molecule, reacts the title complex generated often have premium properties that is optical, electrical, the aspect such as magnetic and catalysis with transition metal.The weak interaction of the non covalent bonds such as the pi-pi accumulation effect formed by the aroma system of pyridine and hydroxy-benzoic acid and intermolecular hydrogen bonding, can assemble many multidimensional super molecular complexes with novel structure and specific function by simple monokaryon small molecule partner.Have changeable coordination mode containing the polydentate ligand enriching hapto, such part and reacting metal salt usually can obtain the netted ligand polymer of multidimensional with novel topology.Nitrogen-atoms there is a lone electron pair, can as good electron donor, Sauerstoffatom there are two lone electron pairs simultaneously, also can as good electron donor, and nitrogen heterocycles and hydroxy-benzoic acid class organic ligand of a great variety, the complex structure obtained is novel, excellent property, so receive the very big concern of people all the time.Pyridine is typical Nitrogen-Containing Heterocyclic Ligand, and hydroxy-benzoic acid has excellent conjugacy, proton acceptability and coordination selectivity etc. simultaneously, is easy to form the super molecular compound with one dimension, two dimension, three-dimensional net structure with metal.
Summary of the invention
The object of this invention is to provide a kind of two (pyridine)-(4-HBA)-chloro-zinc (II) title complex title complex and preparation method thereof, this thermal analysis is good, and preparation technology is simple and easy to operate, productive rate is high, reproducible.
The present invention by the following technical solutions for achieving the above object: a kind of two (pyridine)-(4-HBA)-chloro-zinc (II) title complex, the chemical formula of described title complex is [Zn (L
1)
2l
2cl]
n, wherein the span of n is infinitely great, and the chemical formula of this title complex also can be expressed as [Zn (L
1)
2l
2cl]
∞, wherein L
1for pyridine, skeleton symbol is as follows:
L
2for 4-HBA, L
2skeleton symbol is as follows:
；
Described two (pyridine)-(4-HBA)-chloro-zinc (II) title complex is colorless plate N-type waferN, and belong to oblique system, spacer is
p2 1 / n, unit cell parameters is a=10.0944 (15), b=13.637 (2), c=12.6014 (19),
a=90 °, β=105.745 (3) °, γ=90 °, V=1669.6 (4)
3.
Described two (pyridine)-(4-HBA)-chloro-zinc (II) title complex has mononuclear molecule structure, one-dimensional catenary structure is formed by intermolecular hydrogen bonding effect, wherein Metal Zn (II) is centrally located in the coordination environment of a distorted tetrahedral, Zn (II) follows two atom N N1 from two independently Pyridine Molecules, N2 coordination respectively, also has the oxygen coordination on carboxyl in 4-HBA molecule, Cl atom also participates in the coordination of same Zn (II) atom simultaneously, by the structural analysis to carboxyl in complex molecule, electron delocalization is clearly there is in carboxyl.
The preparation method of described two (pyridine)-(4-HBA)-chloro-zinc (II) title complex: adopt solution crystal process, by ZnCl
2, pyridine and 4-HBA add in methanol solution for 1:2:1 ~ 1:4:1, with ZnCl in molar ratio
2for benchmark, every 1mmolZnCl
2the volume of methanol solution is needed to be 3.8 ~ 4.2mL, at room temperature slow evaporation after stirring and dissolving, colorless plate N-type waferN is obtained after 14 ~ 16 days, this monocrystalline is separated, successively through washing, drying treatment, obtain two (pyridine)-(4-HBA)-chloro-zinc (II) title complex.
Beneficial effect of the present invention: two (pyridine)-(4-HBA)-chloro-zinc (II) title complex has good stability, productive rate reaches about 55%, the advantage such as reproducible, and preparation technology is simple and easy to operate, the crystalline material obtained is expected to obtain further research and development application in field of light emitting materials, the purposes of luminescent material is wider, as: photodiode, navigation, instrument dish at quarter, road sign, phosphorescence thermometer etc., luminescent material can powder, monocrystalline, film or the form such as noncrystal use, title complex of the present invention uses in luminescent material with single crystal forms.
Accompanying drawing explanation
Fig. 1 is the coordination environment figure of Zn (II) in two (pyridine)-(4-HBA)-chloro-zinc (II) title complex.
Embodiment
Embodiment 1
The preparation method of two (pyridine)-(4-HBA)-chloro-zinc (II) title complexs of the present embodiment is as follows:
By ZnCl
2(0.136g, 1.0mmol), L
1(0.16ml, 2.0mmol) and L
2(0.138g, 1.0mmol) add in 3.8mL methanol solution, at room temperature slow evaporation after solution stirring, colorless plate N-type waferN is obtained after 14 days, this monocrystalline is separated, successively through with reformation water washing, about 100 DEG C drying treatment, obtain target product, productive rate: 53%, crystal is stable in the air.Ultimate analysis: by theoretical structural formula C
17h
15znClN
2o
3, calculated value: C51.41, H3.81, N7.05%; Measured value: C50.17, H3.98, N7.12%.
Embodiment 2
The preparation method of two (pyridine)-(4-HBA)-chloro-zinc (II) title complexs of the present embodiment is as follows:
By ZnCl
2(0.136g, 1.0mmol), L
1(0.20ml, 2.5mmol) and L
2(0.138g, 1.0mmol) adds in 4mL methanol solution, at room temperature slow evaporation after solution stirring, obtain colorless plate N-type waferN after 15 days, this monocrystalline is separated, successively through washing, drying treatment, obtain target product, productive rate: 56%, crystal is stable in the air.Ultimate analysis: by theoretical structural formula C
17h
15znClN
2o
3, calculated value: C51.41, H3.81, N7.05%; Measured value: C50.54, H4.03, N7.24%.
Embodiment 3
The preparation method of two (pyridine)-(4-HBA)-chloro-zinc (II) title complexs of the present embodiment is as follows:
By ZnCl
2(0.136g, 1.0mmol), L
1(0.24ml, 3.0mmol) and L
2(0.138g, 1.0mmol) adds in 3.9mL methanol solution, at room temperature slow evaporation after solution stirring, obtain colorless plate N-type waferN after 16 days, this monocrystalline is separated, successively through washing, drying treatment, obtain target product, productive rate: 57%, crystal is stable in the air.Ultimate analysis: by theoretical structural formula C
17h
15znClN
2o
3, calculated value: C51.41, H3.81, N7.05%; Measured value: C50.68, H3.90, N7.08%.
Embodiment 4
The preparation method of two (pyridine)-(4-HBA)-chloro-zinc (II) title complexs of the present embodiment is as follows:
By ZnCl
2(0.136g, 1.0mmol), L
1(0.32ml, 4.0mmol) and L
2(0.138g, 1.0mmol) adds in 4.2mL methanol solution, at room temperature slow evaporation after solution stirring, obtain colorless plate N-type waferN after 14 days, this monocrystalline is separated, successively through washing, drying treatment, obtain target product, productive rate: 55%, crystal is stable in the air.Ultimate analysis: by theoretical structural formula C
17h
15znClN
2o
3, calculated value: C51.41, H3.81, N7.05%; Measured value: C51.20, H3.84, N7.16%.
In Example 1 ~ 4, two (pyridine)-(4-HBA)-chloro-zinc (II) title complex of gained characterizes further respectively, and its process is as follows:
(1) crystal structure determination of title complex
Select the single crystal samples of suitable size, on BrukerSMARTCCD diffractometer, adopt the Mo-K ray (λ=0.71073) through graphite monochromator monochromatization to carry out X-ray measurement.Each diffraction data is collected under 100K.Crystalline structure all uses SHELXS (Sheldrick, 2008) program is solved by direct method, and with Fourier techniques expansion, revises by anisotropy, complete matrix method of least squares is finally adopted to use SHELXS (Sheldrick, 2008) program to revise.Whole non-hydrogen atom coordinate is obtained by direct method, hydrogen atom coordinate is obtained by difference Fourier synthesis method, structural parameter are optimized by complete matrix method of least squares, except hydrogen atom adopts isotropy thermal parameter, other atom (except unordered atom) all adopts anisotropy to carry out thermal parameter method.All calculating all uses SHELXS (Sheldrick, 2008) program.Detailed axonometry data are in table 1, and important bond distance and bond angle data are in table 2.Crystalline structure is shown in Fig. 1.
The predominant crystal data of table 1 title complex
Main bond distance's () of table 2 title complex and bond angle (o)
Symmetrical code: (i) x 1/2, y+1/2, z+3/2
Can be seen by above-mentioned statement result, complex crystal of the present invention belongs to oblique system, spacer is P21/n, unit cell parameters is a=10.0944 (15), b=13.637 (2), c=12.6014 (19), a=90 °, β=105.745 (3) °, γ=90 °, V=1669.6 (4) 3.Described title complex is a mononuclear molecule structure, one-dimensional catenary structure is formed by intermolecular hydrogen bonding effect, wherein Metal Zn (II) is centrally located in the coordination environment of a distorted tetrahedral, Zn (II) follows two atom N N1, the N2 coordination respectively from two independently Pyridine Molecules, also has the oxygen coordination on carboxyl in 4-HBA molecule, Cl atom also participates in the coordination of same Zn (II) atom simultaneously, by the structural analysis to carboxyl in complex molecule, in carboxyl, there is electron delocalization clearly.
Above embodiment is only for illustration of content of the present invention, and in addition, the present invention also has other embodiment.But all employings are equal to conversion or the technical scheme that formed of equivalent deformation mode all drops in protection scope of the present invention.
Claims (3)
1. two (pyridine)-(4-HBA)-chloro-zinc (II) title complex, is characterized in that: the chemical formula of described title complex is [Zn (L
1)
2l
2cl]
n, wherein L
1for pyridine, L
2for 4-HBA, n=1, described two (pyridine)-(4-HBA)-chloro-zinc (II) title complex is colorless plate N-type waferN, and belong to oblique system, spacer is
p2 1 / n, unit cell parameters is a=10.0944 (15), b=13.637 (2), c=12.6014 (19),
=90 °, β=105.745 (3) °, γ=90 °, V=1669.6 (4)
3.
2. two (pyridine)-(4-HBA)-chloro-zinc (II) title complex according to claim 1, it is characterized in that: described two (pyridine)-(4-HBA)-chloro-zinc (II) title complex has mononuclear molecule structure, form one-dimensional catenary structure by intermolecular hydrogen bonding effect, wherein Metal Zn (II) is centrally located in the coordination environment of a distorted tetrahedral.
3. the preparation method of two (pyridine)-(4-HBA)-chloro-zinc (II) title complex according to claim 1 and 2, is characterized in that: adopt solution crystal process, by ZnCl
2, pyridine and 4-HBA add in methanol solution for 1:2:1 ~ 1:4:1, with ZnCl in molar ratio
2for benchmark, every 1mmolZnCl
2the volume of methanol solution is needed to be 3.8 ~ 4.2mL, at room temperature slow evaporation after stirring and dissolving, colorless plate N-type waferN is obtained after 14 ~ 16 days, this monocrystalline is separated, successively through washing, drying treatment, obtain two (pyridine)-(4-HBA)-chloro-zinc (II) title complex.
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|---|---|---|---|---|
| CN102942580A (en) * | 2012-12-06 | 2013-02-27 | 洛阳师范学院 | Zinc 5-methyl isophthalate complex and preparation method thereof |
| CN102993220A (en) * | 2012-12-06 | 2013-03-27 | 洛阳师范学院 | 5-bromoisophthalic acid zinc complex and preparation method thereof |
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| CN102942580A (en) * | 2012-12-06 | 2013-02-27 | 洛阳师范学院 | Zinc 5-methyl isophthalate complex and preparation method thereof |
| CN102993220A (en) * | 2012-12-06 | 2013-03-27 | 洛阳师范学院 | 5-bromoisophthalic acid zinc complex and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and Crystal Structure of Two Chain-Like Complexes of Znic,Cobalt with 2-(4′-Chlorine-benzoyl)benzoic Acid and Bipyridine Ligands;LI Xiu-Mei等;《CHINESE JOURNAL OF INORGANIC CHEMISTRY》;20110810;第27卷(第8期);第1659-1663页 * |
| 一个基于5-（2-吡啶基）-3，3′-联（1H-1，2，4-三氮唑）和均四苯甲酸的锌（II）超分子配合物的合成、晶体结构与荧光性质;葛志伟等;《天津师范大学学报（自然科学版）》;20140130;第34卷(第1期);第92-96页 * |
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