CN106397466B - A kind of alternative identification Cr3+Metal-organic framework and preparation method thereof - Google Patents

A kind of alternative identification Cr3+Metal-organic framework and preparation method thereof Download PDF

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CN106397466B
CN106397466B CN201610783032.2A CN201610783032A CN106397466B CN 106397466 B CN106397466 B CN 106397466B CN 201610783032 A CN201610783032 A CN 201610783032A CN 106397466 B CN106397466 B CN 106397466B
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metal
terbium
organic
organic frame
milliliter
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CN106397466A (en
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刘庆燕
王玉玲
周丽娟
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Jiangxi Normal University
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Jiangxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

A kind of alternative identification Cr3+Metal organic frame and preparation method thereof, chemical formula is [TbC17H17NO13S2K], monoclinic system, space group P21/ c, cell parameter are α=90 °, β=91~93 °, γ=90 °, Z=4.The solution have the advantages that：1, the compound obtained can highly selective identification heavy metal ion Cr3+, and monitoring sensitivity is high, minimum monitoring variable can reach 10 in DMF solution‑5MM/milliliter.

Description

A kind of alternative identification Cr3+Metal-organic framework and preparation method thereof
Technical field
The present invention relates to a kind of metal-organic framework and preparation method thereof more particularly to a kind of alternative identification Cr3+From Terbium metal-organic frame and preparation method thereof of son.
Background technology
Metal-organic framework is also known as porous metals-organic coordination polymer, is a kind of very important porous material, It is that coordinate bond and some other weak effect (such as hydrogen bond and π π act on) are passed through by inorganic metal ion and organic ligand Built-up.Metal-organic framework combines inorganic and organic feature, compared to traditional inorganic porous material (as divided Son sieve) not only there is higher stability, but also be easy to cut out and modify.By the organic ligand for selecting different sizes and type Or introduced on ligand different functional groups can Effective Regulation metal-organic framework duct size and channel surfaces Physical and chemical properties, to obtain with specific function metal-organic framework porous material.Currently, metal-has machine frame Frame gas absorption with detach, be catalyzed, the fields such as fluorescence sense and photoelectromagnetic all show good application prospect.Lanthanide ion Shining has many advantages, such as that very narrow transmitting band and (Stokes) displacement of larger stoke and emission lifetime are long, matches accordingly Closing object often has excellent absorption coefficient and efficient ligand-Ln (III) ion energy forwarding function, thus group of the lanthanides coordinates Object is widely used in the research fields such as bio-imaging, solid luminescent material, fluorescence probe sensor.With human production activity The heavy metal ion of middle generation is increasing, and the discharge of heavy metal ion can generate significant damage to the health of environment and the mankind, So it is people's urgent problem to be solved effectively to carry out micro monitoring to heavy metal ion.Lanthanide series metal-organic frame is with it The advantages that highly selective identification, monitoring sensitivity is high, shows huge application potential in terms of heavy metal ion monitoring.It is organic Ligand 3,3 '-disulfonic acid base -4,4 '-biphenyl dicarboxylic acid di-potassium have the phenyl ring of conjugation, strong coordination ability carboxyl and weak match The sulfonic acid group of capability.The luminous energy that 3,3 '--4,4 '-biphenyl dicarboxylic acids of disulfonic acid base with abundant pi-electron are absorbed can have Effect is transferred to lanthanide metal ion, and the carboxyl with strong coordination ability is conducive to construct stable metal-organic framework, and has The sulfonic group of weak coordination ability can be not involved in coordination or part is coordinated and is arranged in the channel surfaces and a huge sum of money of metal-organic framework Belong to ionization and influences the luminescent properties of entire metal-organic framework.
Invention content
The purpose of the present invention is to provide a kind of alternative identification Cr3+Metal-organic framework and preparation method thereof, should Compound can be used as highly selective identification heavy metal ion Cr3+Functional material.
The present invention is achieved like this, it is characterized in that target compound is terbium metal-organic frame, chemical formula is, [Tb·C17H17NO13S2K], monoclinic system, space group P21/ c, cell parameter areα=90 °, β=91~93 °, γ= 90 °, Z=4.
By terbium nitrate and 3,3 '--4,4 '-biphenyl dicarboxylic acids of disulfonic acid base according to 1:1 molar ratio mixing, which is put into, fills 3 Milliliter N, in the vial that the volume of N '-dimethylformamides, 1 milliliter of water and 1 milliliter of ethyl alcohol is 20 milliliters, the amount control of terbium nitrate System is at 14 milligrams or so, and then constant temperature reacts 4 days at 338K, and it is terbium metal-organic frame, yield to obtain colourless bulk crystals About 50%.
Terbium metal-organic frame of the present invention, it is characterized in that being applied to highly selective identification heavy metal ion Cr3+'s Functional material.
The specific reaction equation of the present invention is：
C14H8O10S2K2(3,3 '--4,4 '-biphenyl dicarboxylic acid di-potassium of disulfonic acid base)+Tb (NO3)3+2H2O+C3H7ON (N, N '-dimethylformamides) → TbC17H17NO13S2K+KNO3+2HNO3
It is an advantage of the invention that：
1, the compound obtained can highly selective identification heavy metal ion Cr3+, and monitoring sensitivity is high, in DMF solution In minimum monitoring variable can reach 10-5MM/milliliter；
2, synthetic method is simple, and easy to operate, sufficient raw, low production cost, the yield of compound synthesis are higher, Purity is high and reproducible so that it is suitble to the requirement that extension produces.
Description of the drawings
Fig. 1 is the crystal structure figure of the present invention.
Specific implementation mode
The compound of the present invention [TbC17H17NO13S2K] synthesis：
[Tb·C17H17NO13S2K] it is obtained using the hot method of Conventional solvents, specific reaction equation is：
2C9H7N3O2(4- (1,2,4-1H- triazoles) benzoic acid)+Zn (NO3)2→ [Zn·(C9H6N3O2)2]+2HNO3 (nitric acid)
Concrete operation step is：By terbium nitrate and 3,3 '--4,4 '-biphenyl dicarboxylic acids of disulfonic acid base according to 1:1 molar ratio Example mixing is put into and fills 3 milliliters of N, the vial that the volume of N '-dimethylformamides, 1 milliliter of water and 1 milliliter of ethyl alcohol is 20 milliliters In, the amount of terbium nitrate is controlled at 14 milligrams or so, and then constant temperature reacts 4 days at 338K, and it is terbium gold to obtain colourless bulk crystals Category-organic frame, yield are about 50%.Show that the crystal is target compound through single crystal diffractometer test.
As shown in Figure 1, the crystal parameters of the present invention are：Monoclinic system, space group P21/ c, cell parameter are α=90 °, β=91~93 °, γ= 90 °, Z=4.In heavy metal ion Cr3+A concentration of 10-3In the DMF solution of mM/milliliter, the terbium metal-organic frame Shine and be significantly quenched, and with the Cd of concentration2+、Pb2+、Zn2+、Co2+Ion is but to the luminous shadow of the terbium metal-organic frame It rings less, illustrates the terbium metal-organic frame alternative detection Cr3+.In addition, working as Cr3+Concentration drop to 10-5MM/milli Shining for terbium metal-organic frame still can effectively be quenched when rising, illustrate the terbium metal-organic frame to Cr3+Detection it is sensitive Degree is high.

Claims (3)

1. a kind of terbium metal-organic frame, it is characterized in that chemical formula is [TbC17H17NO13S2K], monoclinic system, space group is P21/ c, cell parameter are α=90 °, β=91~ 93 °, γ=90 °, Z=4.
2. a kind of preparation method preparing terbium metal-organic frame described in claim 1, it is characterised in that specific steps are such as Under：
By terbium nitrate and 3,3 '--4,4 '-biphenyl dicarboxylic acid di-potassiums of disulfonic acid base according to 1:1 molar ratio mixing is put into Sheng There are 3 milliliters of N, in the vial that the volume of N '-dimethylformamides, 1 milliliter of water and 1 milliliter of ethyl alcohol is 20 milliliters, terbium nitrate At 14 milligrams or so, then constant temperature reacts 4 days at 338K, obtains colourless bulk crystals, the as terbium of claim 1 for amount control Metal-organic framework.
3. a kind of purposes of terbium metal-organic frame according to claim 1, which is characterized in that be used for Selective recognition Cr3+。
CN201610783032.2A 2016-05-17 2016-08-30 A kind of alternative identification Cr3+Metal-organic framework and preparation method thereof Expired - Fee Related CN106397466B (en)

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CN108129676B (en) * 2018-01-31 2021-03-30 江西师范大学 Terbium metal-organic framework capable of selectively identifying 1-hydroxypyrene and preparation method thereof
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