CN105949471B - A kind of Zn (II) coordination polymer and the preparation method and application thereof - Google Patents
A kind of Zn (II) coordination polymer and the preparation method and application thereof Download PDFInfo
- Publication number
- CN105949471B CN105949471B CN201610307213.8A CN201610307213A CN105949471B CN 105949471 B CN105949471 B CN 105949471B CN 201610307213 A CN201610307213 A CN 201610307213A CN 105949471 B CN105949471 B CN 105949471B
- Authority
- CN
- China
- Prior art keywords
- isosorbide
- coordination polymer
- nitrae
- tpy
- ndc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3615—Organic materials containing polymers
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention belongs to a kind of Zn (II) coordination polymers and the preparation method and application thereof；The chemical formula of Zn (II) coordination polymer are as follows: { Zn12(Isosorbide-5-Nitrae-NDC)12(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid, phenyl -2 TPY=4-, 2 ': 6 ', 2 "-terpyridyls；Simple to operation with preparation method, product yield is high, can stablize at 130 DEG C or less, and have the anti-saturated absorption performance of very strong third-order nonlinear optical, the third-order nonlinear susceptibility χ of pure material(3)It is 6.46 × 10‑8Esu, the advantages of can be applied to optical Limiting and lasing safety device.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of Zn (II) coordination polymer and preparation method thereof with
Using.
Background technique
With the development of laser technology, constantly expand in the application of military field, such as Laser interferometers and blinding weapon
Human eye and photoelectric sensor device can be attacked, the vision or even human eye of the systems such as photoelectronic reconnaissance, cannon, navigation and guidance can be made
Etc. being interfered, damage is blinding.With the continuous development of this kind of weapon, the degree of automation is continuously improved, what this respect faced
It threatens increasingly severe.Corresponding attention of the safeguard procedures by various countries, laser protective material is in the protection for being directed to this kind of weapon
On have important researching value, become current popular research field.Currently, having put into the most base of lasing safety device of application
In linear optics principle, general using means such as absorption, reflection and diffraction, these protective devices have certain protection to laser
Effect, but there is also many disadvantages, as guard band is narrow, it is seen that light transmission is low, and protection angular range is restricted.At present
Research have shifted towards using nonlinear optics limiting effect and realize lasing safety function.Anti- saturated absorption material has optical Limiting
The advantages that fast response time, linear transmittance is high, and guard band is wide.Therefore, anti-saturated absorption is as a kind of non-linear absorption mistake
Journey is to it is presently believed that generate optical limitation optimal path.The characteristics of anti-saturated absorption is absorption coefficient with incident intensity
Increase and increases, under laser pump (ing), in low light intensity, it is linear that the absorption of medium, which is approximately considered, and under high light intensity, it is situated between
The absorption coefficient of matter increases with the increase of incident intensity, to realize optical Limiting.
In recent years, organic molecule with big pi-conjugated system due to its with nonlinear factor height, fast response time, can
The advantages that plasticity is strong causes the interest of people more and more.The shape after introducing metal ion especially in conjugated system
At complex, often show bigger nonlinear optical property, and it is easy to process, thermal stability is good, laser deflection
It is worth the advantages that high, but also nonlinear response can be improved by changing metal ion or cooperation base, has become people at present
The hot spot studied.Phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls have very big pi-conjugated system, and the N on pyridyl group is former
Son is easy to be coordinated with metal ion, forms metal-pyridine construction unit；In addition, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid is a kind of common
Be used to construct the ligand of coordination polymer.Above-mentioned metal-pyridine construction unit and Isosorbide-5-Nitrae-naphthalenedicarboxylic acid are fitted together,
A kind of coordination polymer containing very big pi-conjugated system can be constructed, but there is presently no three ranks about such compound
Report in terms of the anti-saturated absorption of nonlinear optics.
Summary of the invention
The purpose of the present invention is to overcome the defects in the prior art and it is simple to operation to provide a kind of preparation method, product
High income can be stablized at 130 DEG C or less, and have the anti-saturated absorption performance of very strong third-order nonlinear optical, pure material
Third-order nonlinear susceptibility χ(3)It is 6.46 × 10-8Esu can be applied to a kind of Zn of optical Limiting and lasing safety device
(II) coordination polymer and preparation method thereof.
The object of the present invention is achieved like this: the chemical formula of Zn (II) coordination polymer are as follows: { Zn12(Isosorbide-5-Nitrae-NDC)12
(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid, phenyl -2 TPY=4-, 2 ': 6 ', 2 "-terpyridyls.
The infrared absorption peak of the coordination polymer includes: 3394 (s), 3112 (s), 2970 (w), 1621 (s), 1521
(m), 1440 (m), 1369 (s), 1288 (m), 1240 (m), 1141 (m), 1105 (m), 991 (w), 952 (m), 860 (w), 833
(s), 754 (m), 738 (m), 701 (m), 653 (m), 584 (m)；Coordination polymer is crystallized in rhombic system, P212121Space group,
Cell parameter are as follows:
The structural unit of the coordination polymer includes 12 Zn (II) ions, 12 Isosorbide-5-Nitrae-NDC ions and 12 TPY altogether
Molecule, in structural unit, each Zn (II) ion uses quadrangular pyramid coordination configuration, respectively and in a TPY molecule
Nitrogen-atoms, the oxygen atom ligand in two Isosorbide-5-Nitrae-NDC molecules；Six of them Zn (II) ion, six Isosorbide-5-Nitrae-NDC ions and six
TPY molecule forms A chain structure, and the other three Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form B link
Structure, last three Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form C chain structure, above-mentioned A chain structure, B chain
Structure and C chain structure are mutually intertwined, and form chiral chain structure.
A kind of preparation method of Zn (II) coordination polymer, it is characterised in that: the following steps are included:
Contain Zn (II) transition metal salt, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls, ethyl alcohol and
Distilled water is put into reaction kettle, adjusts pH value by NaOH, capping kettle reacts four days in the environment of 150 DEG C, then
The temperature of mixed liquor in reaction kettle is dropped into room temperature with 5 DEG C per hour of rate, obtains yellow block after filtering constant temperature washing
Shape crystal, by above-mentioned yellow bulk crystals naturally dry in air.In the transition metal salt containing Zn (II)
Molal quantity, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid molal quantity and phenyl -2 4- of Zn (II), the ratio between the molal quantity of 2 ': 6 ', 2 "-terpyridyls are
1:1:2.The transition metal salt containing Zn (II) is one kind of zinc acetate, zinc nitrate hexahydrate, zinc sulfate or zinc chloride.Institute
The volume ratio of the ethyl alcohol and distilled water stated is 1: 1.The pH value range by NaOH adjusting pH value is 3~5.5.
Zn (II) coordination polymer of the present invention passes through the Z- scan method of standard, and in 7 nanoseconds, wavelength is 532 nanometers, 10 hertz
Under lasing condition hereby, the anti-saturated absorption performance of very strong third-order nonlinear optical, the third-order non-linear of pure material are shown
Polarizability χ(3)It is 6.46 × 10-8Esu, numerical value are far longer than the three of reported inorganic semiconductor material and organic copolymer
Rank non-linear susceptibility.In terms of Zn (II) coordination polymer of the invention is applied to optical Limiting device and lasing safety device.
The present invention has preparation method simple to operation, target coordination polymer high income, can be steady at 130 DEG C or less
It is fixed, and there is the anti-saturated absorption performance of very strong third-order nonlinear optical, the third-order nonlinear susceptibility χ of pure material(3)For
6.46×10-8Esu can be applied to optical Limiting and lasing safety device, and Laser interferometers and blinding weapon is effectively prevent to attack people
The advantages of eye and photoelectric sensor device.
Detailed description of the invention
Fig. 1 is the coordination configuration of metal ion and the connection type of ligand in structural unit of the invention；
Fig. 2 is chain chiral in the present invention along the accumulation graph in the direction c；
Fig. 3 is that linear absorption of the present invention in ultraviolet-visible area is composed；
Fig. 4 is that non-linear absorption of the invention is composed.
Specific embodiment
The present invention is a kind of Zn (II) coordination polymer and the preparation method and application thereof, the chemical formula of the coordination polymer
Are as follows: { Zn12(Isosorbide-5-Nitrae-NDC)12(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid, phenyl -2 TPY=4-, 2 ':
6 ', 2 "-terpyridyls.
The infrared absorption peak of the coordination polymer includes: 3394 (s), 3112 (s), 2970 (w), 1621 (s), 1521
(m), 1440 (m), 1369 (s), 1288 (m), 1240 (m), 1141 (m), 1105 (m), 991 (w), 952 (m), 860 (w), 833
(s), 754 (m), 738 (m), 701 (m), 653 (m), 584 (m)；Coordination polymer is crystallized in rhombic system, P212121Space group,
Cell parameter are as follows:
As shown in Figure 1, in Fig. 1 in order to clearly indicate of the invention structural unit in metal ion coordination configuration and match
The connection type of body, therefore all hydrogen atoms are deleted, and hydrone is omitted；The knot of heretofore described coordination polymer
Structure unit includes 12 Zn (II) ions, 12 Isosorbide-5-Nitrae-NDC ions and 12 TPY molecules, each Zn in structural unit altogether
(II) ion all uses quadrangular pyramid coordination configuration, respectively with the nitrogen-atoms in a TPY molecule, in two Isosorbide-5-Nitrae-NDC molecules
Oxygen atom ligand；As shown in Fig. 2, six of them Zn (II) ion, six Isosorbide-5-Nitrae-NDC ions and six TPY molecules form A chain
Structure, the other three Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form B chain structure, last three Zn
(II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form C chain structure, above-mentioned A chain structure, B chain structure and C chain structure
It is mutually intertwined, forms chiral chain structure.
A kind of preparation method of Zn (II) coordination polymer, comprising the following steps: contain Zn (II) transition metal salt, 1,
4- naphthalenedicarboxylic acid, phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls, ethyl alcohol and distilled water are put into reaction kettle, are adjusted by NaOH
PH value, capping kettle react four days in the environment of 150 DEG C, then with 5 DEG C per hour of rate by mixed liquor in reaction kettle
Temperature drop to room temperature, by filtering constant temperature washing after obtain yellow bulk crystals, in air by above-mentioned yellow bulk crystals
Naturally dry.Molal quantity, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid mole of Zn (II) in the transition metal salt containing Zn (II)
Several and phenyl -2 4-, the ratio between molal quantity of 2 ': 6 ', 2 "-terpyridyls are 1: 1: 2.The transition metal salt containing Zn (II)
For one kind of zinc acetate, zinc nitrate hexahydrate, zinc sulfate or zinc chloride.The volume ratio of the ethyl alcohol and distilled water is 1: 1.Institute
Stating and adjusting the pH value range in pH value by NaOH is 3~5.5.
As shown in figure 3, Fig. 3 is that linear absorption of the present invention in ultraviolet-visible area is composed；Zn (II) coordination polymer of the present invention
By standard Z- scan method, in 7 nanoseconds, wavelength is 532 nanometers, under 10 hertz of lasing condition, shows very strong three
The anti-saturated absorption performance of rank nonlinear optics, the third-order nonlinear susceptibility χ of pure material(3)It is 6.46 × 10-8Esu, numerical value are remote
Much larger than the third-order nonlinear susceptibility of reported inorganic semiconductor material and organic copolymer.Zn (II) coordination of the invention
In terms of polymer can be applied to optical Limiting device and lasing safety device.
For the more detailed explanation present invention, the present invention is further elaborated now in conjunction with embodiment.Specific embodiment
It is as follows:
Embodiment one
A kind of Zn (II) coordination polymer and preparation method thereof, the chemical formula of the coordination polymer are as follows: { Zn12(Isosorbide-5-Nitrae-
NDC)12(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid, phenyl -2 TPY=4-, 2 ': 6 ', 2 "-three connection pyrroles
Pyridine.The infrared absorption peak of the coordination polymer includes: 3394 (s), 3112 (s), 2970 (w), 1621 (s), 1521 (m),
1440 (m), 1369 (s), 1288 (m), 1240 (m), 1141 (m), 1105 (m), 991 (w), 952 (m), 860 (w), 833 (s)
754 (m), 738 (m), 701 (m), 653 (m), 584 (m)；Coordination polymer is crystallized in rhombic system, P212121Space group, structure cell
Parameter are as follows:
The structural unit of the coordination polymer includes 12 Zn (II) ions, 12 Isosorbide-5-Nitrae-NDC ions and 12 TPY molecules altogether,
Each Zn (II) ion uses quadrangular pyramid coordination configuration in structural unit, respectively with the nitrogen-atoms in a TPY molecule, two
Oxygen atom ligand in a Isosorbide-5-Nitrae-NDC molecule；Six of them Zn (II) ion, six Isosorbide-5-Nitrae-NDC ions and six TPY molecule shapes
At A chain structure, the other three Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form B chain structures, and last three
Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form C chain structure, above-mentioned A chain structure, B chain structure and C link
Structure is mutually intertwined, and forms chiral chain structure.
A kind of preparation method of Zn (II) coordination polymer, comprising the following steps: contain Zn (II) transition metal salt, 1,
4- naphthalenedicarboxylic acid, phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls, ethyl alcohol and distilled water are put into reaction kettle, are adjusted by NaOH
PH value, capping kettle react four days in the environment of 150 DEG C, then with 5 DEG C per hour of rate by mixed liquor in reaction kettle
Temperature drop to room temperature, by filtering constant temperature washing after obtain yellow bulk crystals, in air by above-mentioned yellow bulk crystals
Naturally dry, yield 65%.Molal quantity, the Isosorbide-5-Nitrae-of Zn (II) in the transition metal salt containing Zn (II)
The molal quantity of naphthalenedicarboxylic acid and phenyl -2 4-, the ratio between molal quantity of 2 ': 6 ', 2 "-terpyridyls are 1: 1: 2；(II) containing Zn
Transition metal salt be zinc acetate, the molal quantity of zinc acetate is 0.2mmol, quality 0.038g；Isosorbide-5-Nitrae-naphthalenedicarboxylic acid mole
Number is 0.2mmol, quality 0.044g；The molal quantity of phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls is 0.4mmol, and quality is
0.12g.The volume ratio of the ethyl alcohol and distilled water is 1: 1, and the volume of the ethyl alcohol is 8mL and the volume of water distilled water is
8mL.The pH value by NaOH adjusting pH value is 5.5, and the NaOH molal quantity used is 0.4mmol, quality 0.016g.
The powder diffraction spectrum that solid is made in the present embodiment is consistent with single crystal structure analysis simulation map, determines that obtained solid is mesh
Mark compound.
Embodiment two
A kind of Zn (II) coordination polymer and preparation method thereof, the chemical formula of the coordination polymer are as follows: { Zn12(Isosorbide-5-Nitrae-
NDC)12(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid, phenyl -2 TPY=4-, 2 ': 6 ', 2 "-three connection pyrroles
Pyridine.The infrared absorption peak of the coordination polymer includes: 3394 (s), 3112 (s), 2970 (w), 1621 (s), 1521 (m),
1440 (m), 1369 (s), 1288 (m), 1240 (m), 1141 (m), 1105 (m), 991 (w), 952 (m), 860 (w), 833 (s)
754 (m), 738 (m), 701 (m), 653 (m), 584 (m)；Polymer crystallization is in rhombic system, P212121Space group, cell parameter
Are as follows: Institute
The structural unit for stating coordination polymer includes 12 Zn (II) ions, 12 Isosorbide-5-Nitrae-NDC ions and 12 TPY molecules altogether, is being tied
Each Zn (II) ion uses quadrangular pyramid coordination configuration in structure unit, respectively with the nitrogen-atoms in a TPY molecule, two
Oxygen atom ligand in Isosorbide-5-Nitrae-NDC molecule；Six of them Zn (II) ion, six Isosorbide-5-Nitrae-NDC ions and six TPY molecules are formed
A chain structure, the other three Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form B chain structure, last three Zn
(II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form C chain structure, above-mentioned A chain structure, B chain structure and C chain structure
It is mutually intertwined, forms chiral chain structure.
A kind of preparation method of Zn (II) coordination polymer, comprising the following steps: contain Zn (II) transition metal salt, 1,
4- naphthalenedicarboxylic acid, phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls, ethyl alcohol and distilled water are put into reaction kettle, are adjusted by NaOH
PH value, capping kettle react four days in the environment of 150 DEG C, then with 5 DEG C per hour of rate by mixed liquor in reaction kettle
Temperature drop to room temperature, by filtering constant temperature washing after obtain yellow bulk crystals, in air by above-mentioned yellow bulk crystals
Naturally dry, yield 68%.Molal quantity, the Isosorbide-5-Nitrae-of Zn (II) in the transition metal salt containing Zn (II)
The molal quantity of naphthalenedicarboxylic acid and phenyl -2 4-, the ratio between molal quantity of 2 ': 6 ', 2 "-terpyridyls are 1: 1: 2.(II) containing Zn
Transition metal salt be zinc nitrate hexahydrate, the molal quantity of zinc nitrate hexahydrate is 0.2mmol, quality 0.06g；Isosorbide-5-Nitrae-naphthalene two
The molal quantity of formic acid is 0.2mmol, quality 0.044g；The molal quantity of phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls is
0.4mmol, quality 0.12g.The volume ratio of the ethyl alcohol and distilled water is 1: 1, and the volume of the ethyl alcohol is 8mL and water
The volume of distilled water is 8mL.The pH value by NaOH adjusting pH value is 3, and the NaOH molal quantity used is 0.4mmol,
Quality is 0.016g.The powder diffraction spectrum that solid is made in the present embodiment is consistent with single crystal structure analysis simulation map, determines
Obtained solid is target compound.
Embodiment three
A kind of Zn (II) coordination polymer and preparation method thereof, the chemical formula of the coordination polymer are as follows: { Zn12(Isosorbide-5-Nitrae-
NDC)12(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid, phenyl -2 TPY=4-, 2 ': 6 ', 2 "-three connection pyrroles
Pyridine.The infrared absorption peak of the coordination polymer includes: 3394 (s), 3112 (s), 2970 (w), 1621 (s), 1521 (m),
1440 (m), 1369 (s), 1288 (m), 1240 (m), 1141 (m), 1105 (m), 991 (w), 952 (m), 860 (w), 833 (s)
754 (m), 738 (m), 701 (m), 653 (m), 584 (m)；Polymer crystallization is in rhombic system, P212121Space group, cell parameter
Are as follows: Institute
The structural unit for stating coordination polymer includes 12 Zn (II) ions, 12 Isosorbide-5-Nitrae-NDC ions and 12 TPY molecules altogether, is being tied
Each Zn (II) ion uses quadrangular pyramid coordination configuration in structure unit, respectively with the nitrogen-atoms in a TPY molecule, two
Oxygen atom ligand in Isosorbide-5-Nitrae-NDC molecule；Six of them Zn (II) ion, six Isosorbide-5-Nitrae-NDC ions and six TPY molecules are formed
A chain structure, the other three Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form B chain structure, last three Zn
(II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form C chain structure, above-mentioned A chain structure, B chain structure and C chain structure
It is mutually intertwined, forms chiral chain structure.
A kind of preparation method of Zn (II) coordination polymer, comprising the following steps: contain Zn (II) transition metal salt, 1,
4- naphthalenedicarboxylic acid, phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls, ethyl alcohol and distilled water are put into reaction kettle, are adjusted by NaOH
PH value, capping kettle react four days in the environment of 150 DEG C, then with 5 DEG C per hour of rate by mixed liquor in reaction kettle
Temperature drop to room temperature, by filtering constant temperature washing after obtain yellow bulk crystals, in air by above-mentioned yellow bulk crystals
Naturally dry, yield 61%.Molal quantity, the Isosorbide-5-Nitrae-of Zn (II) in the transition metal salt containing Zn (II)
The molal quantity of naphthalenedicarboxylic acid and phenyl -2 4-, the ratio between molal quantity of 2 ': 6 ', 2 "-terpyridyls are 1: 1: 2.(II) containing Zn
Transition metal salt be zinc sulfate, the molal quantity of zinc sulfate is 0.2mmol, quality 0.036g；Isosorbide-5-Nitrae-naphthalenedicarboxylic acid mole
Number is 0.2mmol, quality 0.044g；The molal quantity of phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls is 0.4mmol, and quality is
0.12g.The volume ratio of the ethyl alcohol and distilled water is 1: 1, and the volume of the ethyl alcohol is 8mL and the volume of water distilled water is
8mL.The pH value by NaOH adjusting pH value is 4.2, and the NaOH molal quantity used is 0.4mmol, quality 0.016g.
The powder diffraction spectrum that solid is made in the present embodiment is consistent with single crystal structure analysis simulation map, determines that obtained solid is target
Compound.
Example IV
A kind of Zn (II) coordination polymer and preparation method thereof, the chemical formula of the coordination polymer are as follows: { Zn12(Isosorbide-5-Nitrae-
NDC)12(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid, phenyl -2 TPY=4-, 2 ': 6 ', 2 "-three connection pyrroles
Pyridine.The infrared absorption peak of the coordination polymer includes: 3394 (s), 3112 (s), 2970 (w), 1621 (s), 1521 (m),
1440 (m), 1369 (s), 1288 (m), 1240 (m), 1141 (m), 1105 (m), 991 (w), 952 (m), 860 (w), 833 (s)
754 (m), 738 (m), 701 (m), 653 (m), 584 (m)；Polymer crystallization is in rhombic system, P212121Space group, cell parameter
Are as follows:
The structural unit of the coordination polymer includes 12 Zn (II) ions, 12 Isosorbide-5-Nitrae-NDC ions and 12 TPY molecules altogether,
Each Zn (II) ion uses quadrangular pyramid coordination configuration in structural unit, respectively with the nitrogen-atoms in a TPY molecule, two
Oxygen atom ligand in a Isosorbide-5-Nitrae-NDC molecule；Six of them Zn (II) ion, six Isosorbide-5-Nitrae-NDC ions and six TPY molecule shapes
At A chain structure, the other three Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form B chain structures, and last three
Zn (II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form C chain structure, above-mentioned A chain structure, B chain structure and C link
Structure is mutually intertwined, and forms chiral chain structure.
A kind of preparation method of Zn (II) coordination polymer, comprising the following steps: contain Zn (II) transition metal salt, 1,
4- naphthalenedicarboxylic acid, phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls, ethyl alcohol and distilled water are put into reaction kettle, are adjusted by NaOH
PH value, capping kettle react four days in the environment of 150 DEG C, then with 5 DEG C per hour of rate by mixed liquor in reaction kettle
Temperature drop to room temperature, by filtering constant temperature washing after obtain yellow bulk crystals, in air by above-mentioned yellow bulk crystals
Naturally dry, yield 63%.Molal quantity, the Isosorbide-5-Nitrae-of Zn (II) in the transition metal salt containing Zn (II)
The molal quantity of naphthalenedicarboxylic acid and phenyl -2 4-, the ratio between molal quantity of 2 ': 6 ', 2 "-terpyridyls are 1: 1: 2.(II) containing Zn
Transition metal salt be zinc chloride, the molal quantity of zinc chloride is 0.2mmol, quality 0.026g；Isosorbide-5-Nitrae-naphthalenedicarboxylic acid mole
Number is 0.2mmol, quality 0.044g；The molal quantity of phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls is 0.4mmol, and quality is
0.12g.The volume ratio of the ethyl alcohol and distilled water is 1: 1, and the volume of the ethyl alcohol is 8mL and the volume of water distilled water is
8mL.The pH value by NaOH adjusting pH value is 4.5, and the NaOH molal quantity used is 0.4mmol, quality 0.016g.
The powder diffraction spectrum that solid is made in the present embodiment is consistent with single crystal structure analysis simulation map, determines that obtained solid is target
Compound.
The characterization of structure of the invention is studied, sizeable crystal is chosen in product in example 2, is set
In collection diffracted intensity data on SMART 1K CCD diffractometer.Using the MoK through graphite monochromator monochromatizationαRay, with ω/
φ scanning mode collect diffracted intensity data, test temperature be 25 DEG C, the diffracted intensity data of Zn (II) coordination polymer into
Row LpFactor absorption correction and empirical absorption correction.The initial configuration model analysis calculating of Zn (II) coordination polymer is all made of
SHELXS-97 structure elucidation program is completed by direct method, and is parsed by SELXL-97 structure elucidation program, with complete
Matrix least square method carries out refine to structure.All non-hydrogen atoms are all modified using anisotropic parameters.All Zn
(II) hydrogen atom of coordination polymer is all made of the modes such as theoretical plus hydrogen and handles；Crystallographic parameter and Diffraction Data Collection condition are shown in
Following subordinate list:
The crystallographic data table of Zn (II) coordination polymer
Third-order non-linear of the invention is characterized as below: 30 milligrams in example IV of the present invention weighed, is placed in mortar,
Carefully grinding is until the grain diameter of solid less than 1 micron, tests the solid diffusing reflectance spectra of compound, as shown in figure 3, really first
Determine the linear absorption of compound, compound has stronger absorption in 568 nanometers as the result is shown, and the absorption of the present invention here deviates
532 nanometers of the wavelength of laser in experiment, therefore, which is not susceptible to RESONANCE ABSORPTION.
The compounds of this invention for weighing 30 milligrams in embodiment three, is placed in mortar, carefully of the grinding up to solid
Grain partial size is less than 1 micron.It is dispersed solid in 10 milliliters of ethyl alcohol with ultrasonic unit, passes through conventional spin-on process (spin coating instrument
2000 turns of revolving speed), sample is spin-coated on titanium dioxide silicon substrate slide, using the thickness of thickness gauge measurement coating, is prepared with a thickness of 2
The film of micron.The titanium dioxide silicon substrate slide that thickness of sample is 2 microns that is coated with of above-mentioned preparation is placed in third-order non-linear light
Learn the third order non-linear optical property that compound is tested on tester.Laser used in experiment be 7 nanoseconds, 10 hertz, wave
532 nanometers long, the power density being irradiated on sample is 0.0167Gw/cm2.As shown in figure 4, the present invention presents very strong three
The anti-saturated absorption of rank nonlinear optics, the third-order nonlinear susceptibility χ of pure material(3)It is 6.46 × 10-8esu。
The series of detailed descriptions listed above only for feasible embodiment of the invention specifically
Protection scope bright, that they are not intended to limit the invention, it is all without departing from equivalent implementations made by technical spirit of the present invention
Or change should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of Zn (II) coordination polymer, it is characterised in that: the chemical formula of the coordination polymer are as follows: { Zn12(Isosorbide-5-Nitrae-NDC)12
(TPY)12·2H2O}n；Wherein, Isosorbide-5-Nitrae-NDC=1,4- naphthalenedicarboxylic acid anion, phenyl -2 TPY=4-, 2 ': 6 ', 2 "-three connection pyrroles
Pyridine.
2. a kind of Zn (II) coordination polymer according to claim 1, it is characterised in that: the infrared suction of the coordination polymer
Receiving peak includes: 3394 (s), 3112 (s), 2970 (w), 1621 (s), 1521 (m), 1440 (m), 1369 (s), 1288 (m), 1240
(m), 1141 (m), 1105 (m), 991 (w), 952 (m), 860 (w), 833 (s), 754 (m), 738 (m), 701 (m), 653 (m)
584(m)；Coordination polymer is crystallized in rhombic system, P212121Space group, cell parameter are as follows:
3. a kind of Zn (II) coordination polymer according to claim 1, it is characterised in that: the structure list of the coordination polymer
Member altogether include 12 Zn (II) ions, 12 Isosorbide-5-Nitrae-NDC ions and 12 TPY molecules, in structural unit each Zn (II) from
Son all uses quadrangular pyramid coordination configuration, and respectively with the nitrogen-atoms in a TPY molecule, the oxygen in two Isosorbide-5-Nitrae-NDC molecules is former
Son coordination；Six of them Zn (II) ion, six Isosorbide-5-Nitrae-NDC ions and 6 TPY molecules form A chain structure, the other three Zn
(II) ion, three Isosorbide-5-Nitrae-NDC ions and three TPY molecules form B chain structure, last three Zn (II) ion, three Isosorbide-5-Nitraes-
NDC ion and three TPY molecules form C chain structure, and above-mentioned A chain structure, B chain structure and C chain structure are mutually intertwined, shape
At chiral chain structure.
4. a kind of preparation method of Zn as claimed in any one of claims 1-3 (II) coordination polymer, it is characterised in that: packet
Include following steps:
The transition metal salt for containing Zn (II), Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, phenyl -2 4-, 2 ': 6 ', 2 "-terpyridyls, ethyl alcohol and distillation
Water is put into reaction kettle, adjusts pH value by NaOH, capping kettle reacts four days in the environment of 150 DEG C, then with every
The temperature of mixed liquor in reaction kettle is dropped to room temperature by the rate of 5 DEG C of hour, and it is blocky brilliant to obtain yellow after filtering constant temperature washing
Body, by above-mentioned yellow bulk crystals naturally dry in air.
5. a kind of preparation method of Zn (II) coordination polymer according to claim 4, it is characterised in that: described contains Zn
(II) molal quantity, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid molal quantity and phenyl -2 4- of the Zn (II) in transition metal salt, 2 ': 6 ', 2 "-three
The ratio between molal quantity of bipyridyl is 1: 1: 2.
6. a kind of preparation method of Zn (II) coordination polymer according to claim 4 or 5, it is characterised in that: described
Transition metal salt containing Zn (II) is one kind of zinc acetate, zinc nitrate hexahydrate, zinc sulfate or zinc chloride.
7. a kind of preparation method of Zn (II) coordination polymer according to claim 4, it is characterised in that: the ethyl alcohol
Volume ratio with distilled water is 1: 1.
8. a kind of preparation method of Zn (II) coordination polymer according to claim 4, it is characterised in that: described to pass through
The pH value range that NaOH is adjusted in pH value is 3~5.5.
9. a kind of Zn as described in claim 1 (II) coordination polymer is applied to the anti-saturated absorption material of third-order non-linear.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610307213.8A CN105949471B (en) | 2016-05-05 | 2016-05-05 | A kind of Zn (II) coordination polymer and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610307213.8A CN105949471B (en) | 2016-05-05 | 2016-05-05 | A kind of Zn (II) coordination polymer and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105949471A CN105949471A (en) | 2016-09-21 |
| CN105949471B true CN105949471B (en) | 2018-12-21 |
Family
ID=56911182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610307213.8A Expired - Fee Related CN105949471B (en) | 2016-05-05 | 2016-05-05 | A kind of Zn (II) coordination polymer and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105949471B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544737B (en) * | 2016-10-26 | 2019-03-29 | 辽宁石油化工大学 | A kind of preparation method of U-shaped asymmetric nonlinear optics Inorganic-Organic Hybrid Material |
| CN106496586B (en) * | 2016-10-31 | 2019-04-30 | 淮南师范学院 | A kind of NO free radical magnetism coordination polymer and preparation method thereof |
| CN108794759B (en) * | 2018-08-27 | 2020-11-03 | 江苏科技大学 | Zinc-based luminescent metal organic framework material and preparation method and application thereof |
| CN109320730B (en) * | 2018-09-21 | 2021-04-16 | 重庆师范大学 | Barium-organic coordination polymer, preparation method thereof and application thereof in ion detection and green light composite film preparation |
| CN110504110B (en) * | 2019-08-21 | 2021-09-07 | 河海大学 | Method for preparing supercapacitor by using multi-connected pyridyl metal organic framework Ni-MOF |
| CN110600272B (en) * | 2019-08-21 | 2022-02-22 | 河海大学 | Synthesis method of nickel-based metal organic framework material capable of being used as supercapacitor |
| CN111961215B (en) * | 2020-08-11 | 2022-04-05 | 盐城工学院 | Light-emitting metal-organic framework material based on PBP and dicarboxylic acid ligand and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180895A (en) * | 2011-03-29 | 2011-09-14 | 南昌航空大学 | Metal zinc organic coordination polymer and preparation method thereof |
| WO2014054955A1 (en) * | 2012-10-05 | 2014-04-10 | Politechnika Warszawska | A method for preparing microporous mof materials |
-
2016
- 2016-05-05 CN CN201610307213.8A patent/CN105949471B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180895A (en) * | 2011-03-29 | 2011-09-14 | 南昌航空大学 | Metal zinc organic coordination polymer and preparation method thereof |
| WO2014054955A1 (en) * | 2012-10-05 | 2014-04-10 | Politechnika Warszawska | A method for preparing microporous mof materials |
Non-Patent Citations (3)
| Title |
|---|
| 4"-(3-甲氧基-4-羟基苯基)-2，2":6",2""-三联吡啶及其铜/锌配合物的合成/结构和性质;董才富 等;《无机化学学报》;20141203;第30卷(第12期);第2796-2802页 * |
| Enhanced third-order nonlinear optical properties of three 2D coordination polymers based on bis(imidazole) ligands and dicarboxylic ligands;Run-Qiang Liu等;《Polyhedron》;20160316;第111卷;第16–25页 * |
| Syntheses,structures and third-order nonlinear optical properties of three coordination polymers based on bis(imidazol-l-yl-methyl)benzene and aromatic dicarboxylic ligands;Ning Zhao等;《Polyhedron》;20141002;第85卷;第607–614页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105949471A (en) | 2016-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105949471B (en) | A kind of Zn (II) coordination polymer and the preparation method and application thereof | |
| Keshavarz et al. | Tracking Structural Phase Transitions in Lead‐Halide Perovskites by Means of Thermal Expansion | |
| Yeon et al. | A3V5O14 (A= K+, Rb+, or Tl+), new polar oxides with a tetragonal tungsten bronze related structural topology: synthesis, structure, and functional properties | |
| US10575476B2 (en) | Reflective articles and methods for increasing photosynthesis | |
| Zou et al. | ACdCO 3 F (A= K and Rb): new noncentrosymmetric materials with remarkably strong second-harmonic generation (SHG) responses enhanced via π-interaction | |
| Miskowski et al. | Electronic and vibrational spectra of Ru2 (carboxylate) 4+ complexes. Characterization of a high-spin metal-metal ground state | |
| Gao et al. | Fabrication of a water-stable luminescent MOF with an open Lewis basic triazolyl group for the high-performance sensing of acetone and Fe 3+ ions | |
| Dhanaraj et al. | Investigations on crystal growth, structural, optical, dielectric, mechanical and thermal properties of a novel optical crystal: Nicotinium nitrate monohydrate | |
| Grimm et al. | Dual stimuli-responsive P (NIPAAm-co-SPA) copolymers: synthesis and response in solution and in films | |
| Matsunuma et al. | Doping incompatible elements into calcite through amorphous calcium carbonate | |
| Zhang et al. | Healable, phase-selective, and white-light-emitting titania based hybrid lanthanide-doped metallogels | |
| Revathi et al. | Antibacterial activity and physico-chemical properties of metal-organic single crystal: zinc (Tris) thiourea chloride | |
| Fedoruk et al. | [Methylhydrazinium] 2PbCl4, a two-dimensional perovskite with polar and modulated phases | |
| Zhang et al. | Large third-order optical nonlinearity of two cubane-like clusters containing oxotrithiometalate anions and silver: synthesis, characterization, reactivity, and NLO properties–structure correlation | |
| Kabański et al. | Metal–Organic Framework Optical Thermometer Based on Cr3+ Ion Luminescence | |
| Kim et al. | Geometric change of a thiacalix [4] arene supramolecular gel with volatile gases and its chromogenic detection for rapid analysis | |
| Jiao et al. | A notable reversible thermochromic (3, 3-difluoropyrrolidinium) 2 [CuCl4] with ferroelectricity and ferroelasticity | |
| Zhang et al. | Fabrication of two luminescent imidazolyl cadmium-organic frameworks and their sensing mechanism for 2, 6-dichloro-4-nitroaniline | |
| Helina et al. | Structural, optical, thermal, Mechanical and dielectrical characterizations of γ-glycine crystals grown in strontium chloride solution | |
| CN110590646A (en) | Antimony-based hybrid semiconductor material and synthesis and application thereof | |
| Nordquest et al. | Metal-metal interactions in linear chains. The structure and characterization of bis (pyridine-2-carboxaldoximinato) platinum (II) dihydrate | |
| Kovrugin et al. | pH controlled pathway and systematic hydrothermal phase diagram for elaboration of synthetic lead nickel selenites | |
| Bas et al. | Bilayer thin films that combine luminescent and spin crossover properties for an efficient and reversible fluorescence switching | |
| Priyadharshini et al. | Doped potassium dihydrogen phosphate single crystals with enhanced second-harmonic generation efficiency: an investigation of phase purity, nonlinear, piezoelectric, optical, and crystalline qualities | |
| CN106083937B (en) | Double imidazole radicals metal framework compounds of a kind of Co and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181221 Termination date: 20190505 |