CN105646899A - Metal organic anion framework based on InIII and preparation method and application thereof - Google Patents
Metal organic anion framework based on InIII and preparation method and application thereof Download PDFInfo
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- CN105646899A CN105646899A CN201610037982.0A CN201610037982A CN105646899A CN 105646899 A CN105646899 A CN 105646899A CN 201610037982 A CN201610037982 A CN 201610037982A CN 105646899 A CN105646899 A CN 105646899A
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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
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- C08G83/008—Supramolecular polymers
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- 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
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
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- 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 invention relates to a metal organic anion framework based on InIII and a preparation method and application thereof. According to the technical scheme, In(NO3)3, 2',3,3',5,5',5''hexa-carboxyl terphenyl, a mixed solution of N,N-dimethyl formamide and acetonitrile as a solvent, and a nitric acid solution are added to a container, and stirring is conducted for 30 min at normal temperature; the container is sealed, then placed in an oven and kept for 3 days at the temperature of 358 K; slow cooling to room temperature is conducted, and a colorless transparent rod-shaped crystal is obtained; the colorless transparent rod-shaped crystal is washed with N,N-dimethyl formamide, filtered and dried, and the target product is obtained. The prepared metal organic anion framework based on InIII shows a good fluorescent property and has excellent selectivity for nitrobenzene.
Description
Technical field
The present invention relates to a kind of based on In��The preparation method of metal organic anion skeleton and application, specifically, relate to a kind of have fluorescence activity based on In��The preparation of metal organic anion skeleton and application.
Background technology
Metal organic framework compound (MOFs) is by the coordination polymer of the multiple tooth organic ligand (being fragrance polyacid or polybase mostly) of oxygen-containing, nitrogen etc. with metal ion self assembly. As novel porous crystalline material, metal organic framework compound has the porosity (up to 90%) of superelevation and specific surface area (more than 6000m2/ g), abundant topological structure and its controllability, Scalability, making this material at clean energy resource (mainly as gas such as hydrogen and methane storage medium), the aspect such as adsorbing separation, purification (as high efficiency adsorbent) has potential using value. This material has optical, electrical, magnetic, the catalysis characteristics of uniqueness simultaneously. As a kind of novel porous solid-state material, owing to it is widely applied value, more should understand its architectural characteristic in depth, from the intermolecular interaction of its microcosmic and arrangement, the special nature that some regular collection of profound understanding shows, has important scientific meaning.
Traditional inorganic and organic fluorescence materials is explored widely by various countries' research worker, and inorganic and organic group can show the photoluminescent property of different characteristics respectively. And inorganic interaction with organic group can produce new photoluminescent property. Usually MOFs material is constructed jointly by inorganic metal ion and organic ligand, and therefore MOFs is a selection preferably as fluorescent material. The photoluminescent property of MOFs is limited primarily by the impact of the feature of structure, the coordination environment of metal ion, hole surface character. Nitrobenzol is widely used in the organic synthesis industry such as production dyestuff, spice, explosive, and boiling point is higher, and the evaporation rate under natural conditions is relatively slow, reacts with strong oxidizer and generates the compound that mechanical shock is very sensitive, can form explosive mixture with air. Therefore, fluoroscopic examination Nitrobenzol is significant for the safety of daily production and the process of explosion accident qualitatively.
Summary of the invention
It is an object of the invention to utilize In as metal node, utilize 2', 3,3 ", 5,5', 5 " and six carboxyl terphenyls are as organic ligand, and at a certain temperature, the method synthesis utilizing solvent thermal is a kind of based on In��Metal organic anion skeleton.
The technical solution used in the present invention is: a kind of based on In��Metal organic anion skeleton, comprise the following steps:
1) by In (NO3)3, 2', 3,3 ", 5,5', 5 " six carboxyl terphenyls, acetonitrile, DMF, nitric acid adds in container, under room temperature, stirring;
2) by putting into after seal of vessel in baking oven, under 353-363K, keep 3-4 days; Preferably, heating rate is 2-4 DEG C of min-1��
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains water white transparency rhabdolith; Preferably, the rate of temperature fall being slowly cooled to room temperature is 4-6 DEG C of h-1, and at room temperature stand at least 24 hours.
4) wash with DMF, filter, dry, obtain target product.
Beneficial effects of the present invention: prepared by the present invention based on In��Metal organic anion skeleton in ultraviolet, visibility region, there is stronger fluorescent absorption, it is possible to chemiluminescence imaging detection need not carried out when light source, thus can apply in multiple fields such as biological, chemical as fluorescent probe. It addition, through experiment, prepared by the present invention based on In��Metal organic anion skeleton can detect Nitrobenzol qualitatively, explosive detection in the future is had very good meaning. The present invention based on In��Metal organic anion skeleton preparation method simple, fluorescence intensity is high, has great application prospect.
Accompanying drawing explanation
Fig. 1 be embodiment 1 preparation based on In��The structure chart of metal organic anion skeleton elementary cell
Fig. 2 be embodiment 1 preparation based on In��Metal organic anion skeleton a direction of principal axis schematic diagram.
Fig. 3 be embodiment 1 preparation based on In��Metal organic anion skeleton c-axis direction schematic diagram.
Fig. 4 be embodiment 1 preparation based on In��The Solid fluorescene spectrum figure of metal organic anion skeleton.
Fig. 5 be embodiment 1 preparation based on In��Metal organic anion skeleton fluorescent liquid spectrogram in different solutions.
Detailed description of the invention
Embodiment 1 is based on In��Metal organic anion skeleton
By the In (NO of 0.016mmol3)3, 0.015mmol's, 2', 3,3 ", 5,5', 5 " and six carboxyl terphenyls, the DMF (DMF) of 1ml, the acetonitrile of 0.5ml, the nitric acid of 0.15ml adds in the vial that volume is 5ml, and normal temperature condition stirs 30 minutes. Vial good seal is put in baking oven. Heating makes the temperature of baking oven reach 358K from room temperature, and heating rate is 5 DEG C of min-1, and maintain the temperature at insulation 72 hours under this condition. With 5 DEG C of h-1Rate of temperature fall be slowly cooled to room temperature, obtain water white transparency rhabdolith; With N, N '-dimethyl Methanamide (DMF) solution washing, filtration also dry in atmosphere, are target product, based on In��Metal organic anion skeleton, productivity is 45%.
The present invention synthesis based on In��Metal organic anion skeleton structure as Figure 1-Figure 4, this crystal structure belongs to tetragonal crystal system, and space group is P42/ mmc. Molecular formula is: (Me2NH2)[In(H2L)] (L is 2', 3,3 ", 5,5', 5 " six carboxyl terphenyls). This compound is by monokaryon [In (O2CR)4] as the node three dimensional structure by six carboxyl ligand bridgings. Each In��Center adopts the geometry of eight-coordinate, is formed the tetrahedral structure of four nodes by four hydroxy-acid groups. Each part is in conjunction with four independent In��It is centrally formed a foursquare two dimensional surface, and there is the structure of a complete PtS type.Along c-axis direction, square channel diameter is approximatelyBy by four In between these ducts��The square that center forms with four parts is connected, it is possible to observe on a, b direction of principal axis. Solvent molecule in duct is high degree of dispersion, and voidage reaches 63.6% through PLATON/SOLV estimation.
Embodiment 2 one kinds is based on In��The fluoroscopic examination of metal organic anion skeleton
1. at room temperature determine based on In��The solid powder fluorescence of metal organic anion skeleton, result as shown in Figure 4, from Fig. 4, it can be seen that under the exciting that wavelength is 275nm and 363nm, based on In��Metal organic anion skeleton be that 420nm place shows strong fluorescence emission peak at wavelength.
2. take 100mg based on In��Metal organic anion skeleton crystal, be respectively put in toluene, chlorobenzene, bromobenzene, o-Dimethylbenzene and nitrobenzene solution, through ultrasonic dissolution. Measure the fluorescent liquid spectrum of 400nm to 600nm respectively.
Experimental result is Fig. 5 such as, in toluene, chlorobenzene, bromobenzene and o-Dimethylbenzene, based on In��Metal organic anion skeleton crystal have stronger fluorescence emission peak, and the very overly soft pulse of fluorescence emission peak in nitrobenzene is to being almost 0. This illustrate the present invention based on In��Metal organic anion skeleton have extraordinary selectivity for Nitrobenzol, can detect by p-nitrophenyl qualitatively.
Claims (7)
1. one kind based on In��Metal organic anion skeleton, it is characterised in that: preparation method comprises the steps:
1) by In (NO3)3, 2', 3,3 ", 5,5', 5 " six carboxyl terphenyls, acetonitrile, DMF, nitric acid adds in container, under room temperature, stirring;
2) by putting into after seal of vessel in baking oven, under 353-363K, keep 3-4 days;
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains crystal;
4) wash with DMF, filter, dry, obtain target product.
2. according to claim 1 based on In��Metal organic anion skeleton, it is characterised in that: described based on In��Metal organic anion skeleton, its crystal belongs to tetragonal crystal system, and space group is P42/mmc��
3. according to claim 1 and 2 based on In��Metal organic anion skeleton, it is characterised in that: step 1) in the volume ratio of acetonitrile and DMF be 1:0.5.
4. according to claim 1 and 2 based on In��Metal organic anion skeleton, it is characterised in that: step 2) in, will put into after seal of vessel in baking oven, heating rate is 2-4 DEG C of min-1��
5. according to claim 1 and 2 based on In��Metal organic anion skeleton, it is characterised in that: the described rate of temperature fall being slowly cooled to room temperature is 4-6 DEG C of h-1, and at room temperature stand at least 24 hours.
6. described in claim 1 based on In��Metal organic anion skeleton as fluorescent probe detection Nitrobenzol in application.
7. application according to claim 6, it is characterised in that method is as follows: take described in claim 1 based on In��Metal organic anion skeleton crystal, put in nitrobenzene solution, through ultrasonic dissolution, measure the fluorescent liquid spectrum of 400nm to 600nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110575818A (en) * | 2019-08-06 | 2019-12-17 | 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 |
|---|
| XIU-YAN WAN 等: "Rapid and discriminative detection of nitro aromatic compounds with high sensitivity using two zinc MOFs synthesized through a temperature-modulated method", 《J. MATER. CHEM. A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110575818A (en) * | 2019-08-06 | 2019-12-17 | 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 |
| 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 |
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