CN106893576B - A kind of hybrid inorganic-organic thermal discoloration compound - Google Patents
A kind of hybrid inorganic-organic thermal discoloration compound Download PDFInfo
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- CN106893576B CN106893576B CN201710080910.9A CN201710080910A CN106893576B CN 106893576 B CN106893576 B CN 106893576B CN 201710080910 A CN201710080910 A CN 201710080910A CN 106893576 B CN106893576 B CN 106893576B
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- picoline
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000002845 discoloration Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000004065 semiconductor Substances 0.000 claims abstract description 33
- 238000009396 hybridization Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- -1 (4- dimethylaminostyryl) picoline bromine Compound Chemical class 0.000 claims description 17
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000003053 piperidines Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims description 3
- 241000736199 Paeonia Species 0.000 claims description 3
- 235000006484 Paeonia officinalis Nutrition 0.000 claims description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- UJNFDSOJKNOBIA-UHFFFAOYSA-M 4-[4-(dimethylamino)styryl]-N-methylpyridinium iodide Chemical compound [I-].C1=CC(N(C)C)=CC=C1\C=C\C1=CC=[N+](C)C=C1 UJNFDSOJKNOBIA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000007777 multifunctional material Substances 0.000 claims description 2
- 230000000638 stimulation Effects 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000031709 bromination Effects 0.000 description 15
- 238000005893 bromination reaction Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 230000008859 change Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- LAPLHHHBDSLAOO-UHFFFAOYSA-N I(=O)(=O)O.CN(C1=CC=C(C=CC2=CC(=NC=C2)C)C=C1)C Chemical compound I(=O)(=O)O.CN(C1=CC=C(C=CC2=CC(=NC=C2)C)C=C1)C LAPLHHHBDSLAOO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- BKFNEOXRGFXAML-UHFFFAOYSA-N 2-methylpyridin-1-ium;bromide Chemical compound Br.CC1=CC=CC=N1 BKFNEOXRGFXAML-UHFFFAOYSA-N 0.000 description 1
- GQWAOUOHRMHSHL-UHFFFAOYSA-N 4-ethenyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(C=C)C=C1 GQWAOUOHRMHSHL-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
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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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The present invention relates to a kind of thermal discoloration compounds of inorganic-organic hybridization, it is characterised in that: the chemical formula of the compound is C32H10N4SbBr5.The present invention is a kind of thermochromism hybrid inorganic-organic semiconductor material, and the compound synthesis method is simple, low in cost, reaction condition is mild, calorifics stabilization is higher.In temperature-rise period, which absorbs cut-off side from 570nm and is increased to 800nm at 25 DEG C to 227 DEG C.The material has good photoelectric properties, and in the case where changing color, and huge variation occurs for photoelectric properties.It can stablize and apply to 250 degrees Celsius or less.
Description
Technical field
The present invention relates to a kind of thermochromism semiconductor materials of hybrid inorganic-organic, belong to field of functional materials, especially
Be related to 1,3- (4- dimethylamino phenyl) -2,4- (4- picoline)-cyclobutane bromination antimonic salt as semiconductor material and its
Application in terms of photodetection.
Background technique
Semiconductor material is that a kind of have semiconducting behavior (for conductive capability between conductor and insulator, resistivity is about
Within the scope of 1m Ω cm~1G Ω cm), can be used to make the electronic material of semiconductor devices and integrated circuit.Reflection is partly led
It in fundamental property is various extraneous factors physical effect caused by semiconductor such as the effects of light, thermal and magnetic, electricity in body material
And phenomenon, these can be collectively referred to as the semiconductor property of semiconductor material.The basis material for constituting solid electronic device is most
It is semiconductor, exactly the various semiconductor properties of these semiconductor materials assign different type semiconductor devices with different functions
And characteristic.The basic chemical feature of semiconductor material is there is the covalent bond being saturated, the allusion quotation as covalent bonding character between atom
Type is that tetrahedral structure is shown as in lattice structure, so typical inorganic semiconductor material has diamond or zincblende
(ZnS) structure, since the mineral reserve of the earth are compound mostly, the semiconductor material being used widely in early days is all such mine
Object, such as galena (PbS) are used for radio detection, cuprous oxide (Cu very early2O) it is used as dry-type rectifier, silicon carbide
(SiC) rectification effect is also relatively early to be utilized.Selenium (Se) is the elemental semiconductor for finding and being utilized earliest, is once solid
Rectifier and photronic important materials.Novel organic semi-conductor material, stable structure possess brilliant electrology characteristic, and
And it is low in cost, it can be used to manufacture widely used field effect transistor in modern electronic equipment.Organic semiconductor is a kind of
Plastic material, the special construction possessed are conductive by its.In modern electronic equipment, circuit uses transistor controls not
With the electric current between region.However as the development of science and technology, requirement of the people to material is also higher and higher, by variety classes
Material composite material is made by certain process, can make it retain original component the advantages of, overcome the deficiency, and show
Some new performances out.Inorganic-Organic Hybrid Material combines the good characteristic of inorganic material and organic material, is a kind of uniform
Heterogeneous material, therefore widely studied.3 seed types can be divided into according to its combination and the component of composition material.The
One, organic molecule or polymer are simply embedded in inorganic matrix, between inorganic at this time, organic two component (such as by weak force
Van der Waals force, hydrogen bond, electrostatic interaction or hydrophilic-hydrophobic balance) interaction, such as it is most of doping organic dyestuff or enzyme coagulate
Glue belongs to such；Second, by forming the hydridization of molecular level between inorganic component and organic component, there are strong chemical bonds
(such as covalent bond, ionic bond or coordinate bond), the Inorganic-Organic Hybrid Material with Covalent bonding together be mainly inorganic precursor with it is organic
Functional functional group's cohydrolysis and condensation.Inorganic component has the charges of different polarity with organic component each other and can form ionic bond and obtain
Stable hybrid material system.The Inorganic-Organic Hybrid Material matrix and particle combined with coordinate bond is with lone pair electrons and empty rail
The form that road is mutually coordinated generates chemical action and constitutes hybrid material；Third adds in the hybrid material of above two type
When people's organic or inorganic dopant, novel hybrid material is obtained in the embedding people's inorganic-organic hybridization matrix of doping component.Therefore,
Inorganic-Organic Hybrid Material is shown in the fields such as mechanics, calorifics, optics, electricity, catalysis, food packaging, biology, environmental protection
Wide application prospect.
Thermochromic material refers to that some compounds or mixture visible absorption spectra when heated or cooling change
Functional material, it there is color to change with temperature and the characteristic that changes, and the temperature that color change occurs is known as discoloring temperature.This
Kind material is a kind of hot memory function material, is widely used in industrial, weaving, military, printing, treatment health care, diagnosis, building, prevents
The every field such as pseudo- label, daily decoration, aerospace.China the research of thermochromic material is started from the 1960s,
Originally the substantially irreversible thermochromatic material studied, main is also to be used for thermo-color.Into after the eighties, external heat
The research of off-color material tends to develop to low temperature and reversible both direction, a series of new kinds occurs.China is can backheating
Research in terms of cause off-color material is started late, and product development is less, and in application aspect, many is all introduction of foreign technology, knot
Conjunction Domestic Resources are joint to do factory, therefore combines the performance of organic-inorganic semiconductor and thermochromic material, we successfully have developed
A kind of thermochromism hybrid inorganic-organic semiconductor material.
Summary of the invention
One of the objects of the present invention is to provide a kind of organic and inorganic thermal discoloration compounds；
One of the objects of the present invention is to provide a kind of preparation methods of organic and inorganic thermal discoloration compound；
One of the objects of the present invention is to provide a kind of applications of organic and inorganic thermal discoloration compound；
A kind of thermal discoloration compound of inorganic-organic hybridization, the chemical formula of the compound are C16H20N2SbBr5,
Skeleton symbol is
The compound belongs to monoclinic system, space group P2 at room temperature1/c。
The cell parameter of the compound is β=99.313 (6) °, Z=4,
A kind of preparation method of the thermal discoloration compound of inorganic-organic hybridization, includes the following steps:
1) in room temperature, 4- picoline, iodomethane and 4- dimethylaminobenzaldehyde are dissolved in molar ratio for 1:1:1
In methanol, then stirring is to slowly warm up to 65~70 DEG C, is subsequently added into catalyst piperidines back flow reaction 10~12 hours, works as color
Peony is gradually become, through crystallisation by cooling, filtering, drying, obtains 4- (4- dimethylaminostyryl) picoline iodate
Object；
2) under conditions of heating stirring (100 degree of temperature), by step 1) resulting 4- (4- dimethylaminostyrene
Base) picoline bromide and antimony oxide be that 1:1 is added in hydrobromic acid in molar ratio, it reaction 0.5 hour or more, most passes through afterwards
It stands, cooling and crystallization, obtains the compound.
The amount of the piperidines is to add 3-5L piperidines according to the 4- picoline of every 5mol.
A kind of purposes of the thermal discoloration compound of inorganic-organic hybridization, the compound is as warm to response stimulation
The new material of multifunctional material, semiconductor material or photodetection field.
Thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane bromination antimonic salt
Using.
The principle of the present invention is as follows:
(1) variable absorption energy band
1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane bromination antimonic salt thermochromism semiconductor material tool
There are three special energy band variable conditions, and range of temperature is from minus 173 to 227 degrees Celsius.First state be from minus 173 to
117 degrees Celsius, the color of crystal can rapidly carry out reversible switching colourless between yellow；Second state is from 117
To 177 degrees Celsius, crystal is able to achieve from yellow to red variation, but to realize that the red change to yellow is abnormal slowly, closely
Seemingly it is irreversibly changed；Third state is 177 to 227 degrees Celsius, and the color of crystal can be switched in red with black.It is whole
A range of temperature, the structure of material, space group and cell parameter are all without great variation, the reason of causing energy band to change
It is the change of bond distance between Sb-Br.
(2) photoconductive property is tested
Using the photoelectric device test being made by film, the results showed that the organic and inorganic thermochromism semiconductor material
With good semiconducting behavior, great changes have taken place for the light absorption range before and after discoloration.It is heated to the crystal of 125 degree and 175 degree,
Under equal conditions, it is respectively placed under photoelectricity test instrument and is tested, huge variation also has occurred in discovery photoelectric respone.
Compared with the prior art, the invention has the following advantages:
The present invention is a kind of thermochromism hybrid inorganic-organic semiconductor material, and the compound synthesis method is simple, cost
It is cheap, reaction condition is mild, calorifics stabilization it is higher.In temperature-rise period, the material at 25 DEG C to 227 DEG C, absorb cut-off side from
570nm is increased to 800nm.The material has good photoelectric properties, and in the case where changing color, and photoelectric properties occur huge
Big variation.It can stablize and apply to 250 degrees Celsius or less.
Detailed description of the invention
Fig. 1 is the structure and discoloration figure of 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane bromination antimonic salt.
Fig. 2 is the light absorption change curve of 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane bromination antimonic salt.
Fig. 3 is the photoelectric respone curve of 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane bromination antimonic salt.
Fig. 4 is the thermogravimetric analysis signal of 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane bromination antimonic salt
Figure.
Specific embodiment
The content of present invention is described in detail with specific embodiment with reference to the accompanying drawings of the specification, but the present invention is not only
It is limited to following embodiment:
Embodiment 1
Organic and inorganic thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane
The preparation of bromination antimonic salt.
By 4- picoline (5 × 10-3Mol), iodomethane (5 × 10-3) and 4- dimethylaminobenzaldehyde (5 × 10 mol- 3Mol) be dissolved in 50~100mL methanol, stirring is to slowly warm up to 65~70 DEG C, be added 3~5mL piperidines as catalyst into
Row 10~12h of back flow reaction, solution colour gradually become peony by faint yellow, solution after crystallisation by cooling, filtering, drying,
4- (4- dimethylaminostyryl) methyl pyridinium iodide is obtained, 4- (4- dimethylaminostyryl) first is dried to obtain
Pyridinium iodide yield is 80.2%.
Under conditions of heating stirring, by 0.0025 mole of 4- (4- dimethylaminostyryl) picoline iodate
Object and 0.0025 mole of antimony oxide are added in 10~20 milliliters of hydrobromic acid, react about 0.5 hour, obtain clarifying molten
After liquid, by standing, cooling, yellow block-shaped target product, i.e. 1,3- (4- dimethylamino phenyl) -2,4- (methyl pyrrole are crystallized to obtain
Pyridine) cyclobutane bromination antimonic salt, yield 76.4%.Then analysis is carried out by X-ray single crystal diffractometer and obtains crystal structure.Such as
Shown in Fig. 1.
Embodiment 2
Organic and inorganic thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane
The absorption spectrum of bromination antimonic salt.
To 1 obtained organic and inorganic thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2 of case study on implementation,
The test of 4- (picoline) cyclobutane bromination antimonic salt progress thermochromic properties, ultraviolet-ray visible absorbing, as shown in Fig. 2, its
Change colour feature are as follows: in temperature-rise period, material absorbs cut-off side from 570nm and be increased to 800nm at 25 DEG C to 227 DEG C.Therefore, on
Compound is stated as a kind of new absorbing material.
Embodiment 3
Organic and inorganic thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane
The photoconductive property of bromination antimonic salt.
To 1 obtained organic and inorganic thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2 of case study on implementation,
4- (picoline) cyclobutane bromination antimonic salt carries out the test of photoelectric response performance, as shown in figure 3, the material has good photoelectricity
Performance, and in the case where changing color, huge variation occurs for photoelectric properties.
Embodiment 4
Organic and inorganic thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2,4- (picoline) cyclobutane
The thermogravimetric analysis of bromination antimonic salt.
To 1 obtained organic and inorganic thermochromism semiconductor material 1,3- (4- dimethylamino phenyl) -2 of case study on implementation,
4- (picoline) cyclobutane bromination antimonic salt carries out thermogravimetric and differential thermal analysis.It can be found that material can be stablized and apply to 250 and take the photograph
(as shown in Figure 4) below family name's degree.
Claims (6)
1. a kind of thermal discoloration compound of inorganic-organic hybridization, it is characterised in that: the chemical formula of the compound is
C16H20N2SbBr5, skeleton symbol is
2. a kind of thermal discoloration compound of inorganic-organic hybridization according to claim 1, it is characterised in that: described
Compound belongs to monoclinic system, space group P2 at room temperature1/c。
3. a kind of thermal discoloration compound of inorganic-organic hybridization according to claim 2, it is characterised in that: described
The cell parameter of compound is β=
99.313 (6) °, Z=4,
4. a kind of preparation of the thermal discoloration compound of inorganic-organic hybridization described in any one of -3 according to claim 1
Method, characterized by the following steps:
It 1) is in molar ratio that 1:1:1 is dissolved in methanol by 4- picoline, iodomethane and 4- dimethylaminobenzaldehyde in room temperature
In, then stirring be to slowly warm up to 65~70 DEG C, be subsequently added into catalyst piperidines back flow reaction 10~12 hours, when color gradually
Become peony, through crystallisation by cooling, filtering, drying, obtains 4- (4- dimethylaminostyryl) methyl pyridinium iodide；
2) under conditions of temperature is 100 DEG C, by the resulting 4- of step 1) (4- dimethylaminostyryl) picoline bromine
Compound and antimony oxide are that 1:1 is added in hydrobromic acid in molar ratio, are stirred to react 0.5 hour or more, are most stood, cooled down afterwards
And crystallization, obtain the compound.
5. a kind of preparation method of the thermal discoloration compound of inorganic-organic hybridization according to claim 4, feature exist
In: the amount of the piperidines is to add 3-5L piperidines according to the 4- picoline of every 5mol.
6. a kind of purposes of the thermal discoloration compound of inorganic-organic hybridization described in any one of -3 according to claim 1,
It is characterized by:
The compound is as heat to response stimulation multifunctional material, semiconductor material or the novel-section in photodetection field
Material.
Priority Applications (1)
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| 金属有机杂化型相变化合物四氯合锌酸二吡咯烷的设计合成和性质;余国建 等;《科学通报》;20141231;3080-3085 * |
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