CN105646899B - One kind being based on InⅢMetal organic anion skeleton and its preparation method and application - Google Patents
One kind being based on InⅢMetal organic anion skeleton and its preparation method and application Download PDFInfo
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- CN105646899B CN105646899B CN201610037982.0A CN201610037982A CN105646899B CN 105646899 B CN105646899 B CN 105646899B CN 201610037982 A CN201610037982 A CN 201610037982A CN 105646899 B CN105646899 B CN 105646899B
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- 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
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- 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
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- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Abstract
The present invention relates to one kind to be based on InⅢMetal organic anion skeleton and its preparation method and application.The technical solution adopted is that: by In (NO3)3, 2', 3,3 ", 5,5', 5 " six carboxyl terphenyls, solvent is n,N-Dimethylformamide and acetonitrile mixed solution, adds nitric acid solution in container, under room temperature, is stirred 30 minutes；It is put into baking oven after container is sealed, under temperature 358K, is kept for 3 days；It is slowly cooled to room temperature, obtains colorless and transparent rhabdolith；It washed, filtered with n,N-Dimethylformamide, is dry, obtaining target product.Based on In prepared by the present inventionⅢMetal organic anion skeleton shows good photoluminescent property, and p-nitrophenyl has excellent selectivity.
Description
Technical field
The present invention relates to one kind to be based on InⅢThe preparation method and application of metal organic anion skeleton specifically relate to
And it is a kind of with fluorescence activity based on InⅢMetal organic anion skeleton preparation and its application.
Background technique
Metal organic framework compound (MOFs) be by oxygen-containing, nitrogen etc. multiple tooth organic ligand (be mostly fragrant polyacid or
Polybase) with metal ion self assembly made of coordination polymer.As novel porous crystalline material, metal organic framework compound
Porosity (up to 90%) and specific surface area with superelevation are (more than 6000m2/ g), topological structure abundant and it is adjustable
Property, Scalability, make the material at clean energy resource (mainly as gas such as hydrogen and methane storage medium), adsorbing separation mentions
Pure (as high efficiency adsorbent) etc. has potential using value.The material has unique light, electricity, magnetic, catalysis simultaneously
Characteristic.As a kind of novel porous solid-state material, due to its wide application value, its structure spy should be more understood in depth
Property, since its microcosmic intermolecular interaction and arrangement, the special nature that the certain regular collections of profound understanding are showed, tool
There is important scientific meaning.
Traditional inorganic and organic fluorescence materials are widely explored by various countries researcher, inorganic and organic group energy
The photoluminescent property of different characteristics is shown respectively.And the interaction of inorganic and organic group can produce new photoluminescent property.
Generally MOFs material is to be constructed jointly by inorganic metal ion and organic ligand, therefore MOFs is as fluorescent material
Preferable selection.The photoluminescent property of MOFs mainly by structure the characteristics of, the coordination environment of metal ion, hole surface property shadow
It rings.Nitrobenzene is widely used in the organic syntheses industry such as production dyestuff, fragrance, explosive, and boiling point is higher, the evaporation under natural conditions
Speed is slower, reacts with strong oxidizer and generates the compound very sensitive to mechanical shock, can form explosive mixture with air.
Therefore, qualitative fluorescence detection nitrobenzene is of great significance for the safety of daily production and the processing of explosion accident.
Summary of the invention
The purpose of the present invention is utilize 2', 3,3 ", 5,5', 5 " six carboxyl terphenyl conducts using In as metal node
Organic ligand is synthesized a kind of based on In at a certain temperature using the method for solvent heatⅢMetal organic anion skeleton.
The technical solution adopted by the present invention is that: one kind being based on InⅢMetal organic anion skeleton, comprising the following steps:
1) by In (NO3)3, 2', 3,3 ", 5,5', 5 " six carboxyl terphenyls, acetonitrile, n,N-Dimethylformamide, nitric acid adds
Enter in container, under room temperature, stirring；
2) it is put into after sealing container in baking oven, under 353-363K, is kept for 3-4 days；Preferably, heating rate 2-4
℃·min-1。
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains colorless and transparent rhabdolith；Preferably, it progressively cools to
The rate of temperature fall of room temperature is 4-6 DEG C of h-1, and at least 24 hours are stood at room temperature.
4) it is washed, is filtered with n,N-Dimethylformamide, it is dry, obtain target product.
Beneficial effects of the present invention: based on In prepared by the present inventionⅢMetal organic anion skeleton ultraviolet, visible
Region has stronger fluorescent absorption, and chemiluminescence imaging detection can be carried out under conditions of not needing light source, thus can make
It is applied for fluorescence probe in multiple fields such as biology, chemistry.In addition, by experiment, based on In prepared by the present inventionⅢ's
Metal organic anion skeleton can qualitatively detect nitrobenzene, have very good meaning to explosive detection in the future
Justice.It is of the invention based on InⅢMetal organic anion skeleton preparation method it is simple, fluorescence intensity is high, has very big application
Prospect.
Detailed description of the invention
Fig. 1 is the preparation of embodiment 1 based on InⅢMetal organic anion skeleton basic unit structure chart
Fig. 2 is the preparation of embodiment 1 based on InⅢMetal organic anion skeleton a axis direction schematic diagram.
Fig. 3 is the preparation of embodiment 1 based on InⅢMetal organic anion skeleton c-axis direction schematic diagram.
Fig. 4 is the preparation of embodiment 1 based on InⅢMetal organic anion skeleton Solid fluorescene spectrum figure.
Fig. 5 is the preparation of embodiment 1 based on InⅢFluorescent liquid light of the metal organic anion skeleton in different solutions
Spectrogram.
Specific embodiment
Embodiment 1 is based on InⅢMetal organic anion skeleton
By the In (NO of 0.016mmol3)3, 0.015mmol's, 2', 3,3 ", 5,5', 5 " six carboxyl terphenyls, the N of 1ml,
Dinethylformamide (DMF), the acetonitrile of 0.5ml, the nitric acid of 0.15ml is added in the vial that volume is 5ml, and room temperature
Condition stirs 30 minutes.Vial is sealed and is put into baking oven.Heating makes the temperature of baking oven reach 358K, heating speed from room temperature
Rate is 5 DEG C of min-1, and maintain the temperature at and keep the temperature 72 hours under this condition.With 5 DEG C of h-1Rate of temperature fall progressively cool to room
Temperature obtains colorless and transparent rhabdolith；With N, the washing of N '-dimethyl formamide (DMF) solution is filtered and is dried in air,
As target product is based on InⅢMetal organic anion skeleton, yield 45%.
The present invention synthesize based on InⅢMetal organic anion skeleton structure it is as Figure 1-Figure 4, the crystal structure
Belong to tetragonal crystal system, space group P42/mmc.Molecular formula are as follows: (Me2NH2)[In(H2L)] (L 2', 3,3 ", 5,5', 5 " six carboxylics
Base terphenyl).The compound is by monokaryon [In (O2CR)4] tied as node by three-dimensional made of six carboxyl ligand bridgings
Structure.Each InⅢCenter uses the geometry of eight-coordinate, and the tetrahedron knot of four nodes is formed by four carboxylic acid groups
Structure.Four independent In of each ligand bindingⅢIt is centrally formed a square two-dimensional surface, and there is a complete PtS
The structure of type.Along c-axis direction, rectangular channel diameter is aboutBy by four In between these ductsⅢCenter and
The square of four ligands composition is connected, and can observe in a, b axis direction.Solvent molecule in duct is high degree of dispersion
, and voidage reaches 63.6% by PLATON/SOLV estimation.
Embodiment 2 is a kind of to be based on InⅢMetal organic anion skeleton fluorescence detection
1. being determined at room temperature based on InⅢMetal organic anion skeleton solid powder fluorescence, as a result such as Fig. 4 institute
Show, from Fig. 4, it can be seen that in the case where wavelength is the excitation of 275nm and 363nm, be based on InⅢMetal organic anion skeleton exist
Wavelength is to show strong fluorescence emission peak at 420nm.
2. take 100mg based on InⅢMetal organic anion skeleton crystal, be respectively put into toluene, chlorobenzene, bromobenzene, neighbour
In dimethylbenzene and nitrobenzene solution, by ultrasonic dissolution.The fluorescent liquid spectrum of 400nm to 600nm is measured respectively.
Experimental result such as Fig. 5 is based on In in toluene, chlorobenzene, bromobenzene and ortho-xyleneⅢMetal organic anion bone
Frame crystal has a stronger fluorescence emission peak, and fluorescence emission peak in nitrobenzene is very weak or even almost 0.This illustrates this
Invention based on InⅢMetal organic anion skeleton have an extraordinary selectivity for nitrobenzene, can qualitative p-nitrophenyl
It is detected.
Claims (6)
1. one kind is based on InⅢMetal organic anion skeleton, it is characterised in that: preparation method includes the following steps:
1) by In (NO3)3, 2', 3,3'', 5,5', 5'', six carboxyl terphenyl, acetonitrile, n,N-Dimethylformamide, nitric acid addition
In container, under room temperature, stirring；
2) it is put into after sealing container in baking oven, under 353-363K, is kept for 3-4 days；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains crystal；
4) it is washed, is filtered with n,N-Dimethylformamide, it is dry, obtain target product；
It is described based on InⅢMetal organic anion skeleton, molecular formula are as follows: (Me2NH2)[In(H2L)], wherein L be 2', 3,
Six carboxyl terphenyl of 3'', 5,5', 5''；Its crystal belongs to tetragonal crystal system, space group P42/mmc。
2. according to claim 1 be based on InⅢMetal organic anion skeleton, it is characterised in that: acetonitrile in step 1)
Volume ratio with N,N-dimethylformamide is 1:0.5.
3. according to claim 1 be based on InⅢMetal organic anion skeleton, it is characterised in that: in step 2, will hold
It is put into baking oven after device sealing, heating rate is 2-4 DEG C of min-1。
4. according to claim 1 be based on InⅢMetal organic anion skeleton, it is characterised in that: described is slow cold
But the rate of temperature fall for arriving room temperature is 4-6 DEG C of h-1, and at least 24 hours are stood at room temperature.
5. described in claim 1 be based on InⅢMetal organic anion skeleton as fluorescence probe detection nitrobenzene in
Using.
6. application according to claim 5, it is characterised in that method is as follows: taking described in claim 1 based on InⅢGold
Belong to organic anion skeleton crystal, be put into nitrobenzene solution, by ultrasonic dissolution, measures the fluorescent liquid of 400nm to 600nm
Spectrum.
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| CN108191894A (en) * | 2018-01-12 | 2018-06-22 | 辽宁大学 | A kind of metal organic anion framework material formed based on indium and its preparation method and application |
| CN110575818B (en) * | 2019-08-06 | 2022-08-23 | 杭州电子科技大学 | Carboxyl modified ionic metal organic framework material capable of rapidly, efficiently and selectively adsorbing trace pollutants as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
| CN104338556A (en) * | 2013-07-25 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
| CN104338556A (en) * | 2013-07-25 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material |
Non-Patent Citations (1)
| Title |
|---|
| Rapid and discriminative detection of nitro aromatic compounds with high sensitivity using two zinc MOFs synthesized through a temperature-modulated method;Xiu-Yan Wan 等;《J. Mater. Chem. A》;20150925;第3卷;第22369-22376页 |
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