CN109053635A - A kind of application of Organic micromolecular semiconductor material as organic ferromagnetic material - Google Patents
A kind of application of Organic micromolecular semiconductor material as organic ferromagnetic material Download PDFInfo
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- CN109053635A CN109053635A CN201810862683.XA CN201810862683A CN109053635A CN 109053635 A CN109053635 A CN 109053635A CN 201810862683 A CN201810862683 A CN 201810862683A CN 109053635 A CN109053635 A CN 109053635A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
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Abstract
The invention belongs to organo-metallic material field, a kind of application of Organic micromolecular semiconductor material as organic ferromagnetic material is disclosed.The Organic micromolecular semiconductor material has general structure shown in formula (I), and A indicates the conjugation group with electron-withdrawing ability in formula.Organic micromolecular semiconductor material of the present invention has unexpected ferromagnetism, and Curie temperature is very high, so that the material becomes the ferrimagnet haveing excellent performance.
Description
Technical field
The invention belongs to organo-metallic material fields, and in particular to a kind of Organic micromolecular semiconductor material is as Organic Iron
The application of magnetic material.
Background technique
Electronics also carries this intrinsic attribute that spins other than carrying charge.All the time, the development companion of information technology
With the regulation of the charge of spin or semiconductor material to magnetic material.But produce ferromagnetic semiconductor at room temperature always
It is the hang-up for perplexing people.Semiconductor with intrinsic magnetism, refer to external electric field change Fermi surface while, also can be significant
The arrangement for influencing Net magnetic moment, to change macroscopic magnetization.1986, T.Story et al. was carried out in semiconductor PbSnTe system
Mn doping, obtains the non-zero ferromagnetic Curie temperature changed by Influence of Carriers, realizes the reality of first magnetic-doped semiconductor
Test prototype.1991, with the research of p-nitrophenyl nitrate oxide crystal, the organic of no metallic element was had found for the first time
Ferromagnet.1996, Banister et al. had found the sulphur at temperature 36K-nitrogen free radical spontaneous manetization phenomenon.2000,
Ohno and Chiba adulterates Mn element in InAs, finds Modulatory character of the extraordinary Hall effect under electric field action, startles science
Boundary.All the time, room-temperature ferromagnetic material more tends to inorganic metallic materials and Metal-organic complex and yin-yang
Ion doping organic matter, small organic molecule ferrimagnet are seldom reported in this field.Therefore it finds a kind of regulatable steady
Fixed pure organic ferromagnetism molecule, which makes its Curie temperature reach room temperature or more, has intrinsic ferromagnetic semiconductor for finding
It is of great significance.
This patent first invention people is in Journal of Physical Chemistry C, 2017,121,8579-8588
The result of study of middle report shows: the organic semi-conductors molecular structure flatness such as the conjugation small molecule of narrow band gap and polymer compared with
Good, it is resonant that molecule will appear quinoid free radical, generates intrinsic free radical.In solution state, molecule is easy to rotate, and quinoid is free
Base disappears, and shows as fragrant formula structure；When molecule is in solid, especially crystalline state aggregation, molecule blocked rotation, molecule displays go out
Partial quinoid pair/polyradical resonant structure, contributes to the essential structure of molecule, i.e. aggregation inducing free radical
(Aggregation induced radical, AIR).We are from theory and test (the pure good-solvent solution of sample, good solvent
Electron paramagnetic resonance spectrum ESR test with the mixed solvent sample solution, crystal powder sample of poor solvent shows that free radical contains
Amount be sequentially increased) at the same demonstrate AIR mechanism.
Summary of the invention
It is reported in Journal of Physical Chemistry C, 2017,121,8579-8588 based on inventor
Organic micromolecular semiconductor material, we have surprisingly found that the material of acquisition has strong ferromagnetism, and the ferromagnetism embodies
Non-linear relation is presented in the intensity of magnetization and external magnetic field of the Organic micromolecular semiconductor material, under room temperature or even 350K high temperature
Still there is typical hysteresis loop.The purpose of the present invention is to provide a kind of Organic micromolecular semiconductor material as Organic Iron
The application of magnetic material.
The object of the invention is achieved through the following technical solutions:
A kind of application of Organic micromolecular semiconductor material as organic ferromagnetic material, the organic small molecular semiconductor material
Material has general structure shown in formula (I):
A indicates the conjugation group with electron-withdrawing ability in formula.
Preparation with general structure Organic micromolecular semiconductor material as above, can refer to patent early period
CN106397355A。
Preferably, A has following described in any item structures in the formula (I):
Wherein R indicates alkyl.
The free radical stable mechanism of Organic micromolecular semiconductor material of the present invention are as follows: in D-A-D structure, there is electrophilic
The group of ability can make the singlet diradical of the similar Chichibabin free radical of resonant generation steadily delocalization
On the π track of conjugation, on the other hand, the benzoquinones structure by air oxidation or itself resonance generation makes the freedom of triplet state
Base is not easy to again be oxidized inactivation, the similar nitro for inserting two phenyl ring, have it is a variety of resonant, to obtain stabilization
Characteristics of Free Radicals Produced, mechanism is as shown in Figure 1.
The ferromagnetism principle of Organic micromolecular semiconductor material of the present invention are as follows: we are had found for the first time in room temperature and temperatures above
Under excitation, had found in electron paramagnetic resonance (ESR) test using triphenylamine base phenol amine as the D-A-D type small molecule material of donor
Strong stabilization ESR signal, the Series Molecules stabilize free radical, benzoquinones quinone by the conjugated π system delocalization effect of intramolecular
Formula stable structure meta position triplet state free radical (paper early period Journal of Physical Chemistry C is referred to,
2017,121,8579-8588 reports), while the intermolecular identical spin direction arrangement fill characteristic for presenting long-range order, from
And this structure is made to obtain unique ferromagnetism, mechanism is as shown in Figure 2.
Innovation sex expression of the invention is as follows:
(1) Organic micromolecular semiconductor material of the present invention has unexpected stabilized radical and ferromagnetism,
Curie temperature is very high, so that the material becomes the ferrimagnet haveing excellent performance.
(2) Organic micromolecular semiconductor material of the present invention has good thermal stability and optical stability.
(3) Organic micromolecular semiconductor material of the present invention still keeps preferable performance under the conditions of high fever, solvable
Liquid processing is a kind of soft material easily crystallized.
(4) its synthesis of Organic micromolecular semiconductor material of the present invention is simple, and separating-purifying is at low cost, molecular structure
It determines.
Detailed description of the invention
Fig. 1 is the free radical stable mechanism figure of Organic micromolecular semiconductor material of the present invention.
Fig. 2 is the ferromagnetism mechanism figure of Organic micromolecular semiconductor material of the present invention.
Fig. 3 is the alternating temperature electron paramagnetic resonance spectrum figure of Organic micromolecular semiconductor material in embodiment 1.
Fig. 4 is the hysteresis loop figure of Organic micromolecular semiconductor material at different temperatures in embodiment 1.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
According to the embodiment that 106397355 A of patent No. CN is announced, the small molecule material 1 of following structural formula is made
(TPABT-OH):
(1) characterization of small molecule material 1:
5mg sample TPABT-OH is taken to be dissolved in deuterated dimethyl sulfoxide reagent, chemical shift passes through using TMS as internal standard
DRX-400MHz spectrometer (Bruker, Germany) records nucleus magnetic hydrogen spectrum peak at normal temperature.1H NMR(400MHz,DMSO)δ
9.36 (d, J=21.8Hz, 4H), 7.79 (dd, J=27.7,8.1Hz, 4H), 7.52 (dd, J=42.6,7.9Hz, 4H),
7.05-6.94 (m, 9H), 6.78 (td, J=8.3,4.0Hz, 10H).Later, it is small that solution in nuclear magnetic tube is heated to 2 at 160 DEG C
When, retest nuclear-magnetism.As a result as follows:1H NMR(400MHz,DMSO)δ9.38,7.84,7.82,7.77,7.75,7.58,
7.56,7.48,7.46,7.03,7.01,6.99,6.96,6.81,6.79,6.79,6.77,6.76,6.75.Pass through heating front and back
Nuclear magnetic spectrogram compare discovery: Organic micromolecular semiconductor material of the present invention have good thermal stability.
(2) small molecule material 1 tests free radical:
Paramagnetic pipe is added in 10mg sample TPABT-OH in glove box, passes through Bruker ELEXSYS E500 spectrometer
The electron paramagnetic resonance spectrum figure at different temperatures 100K, 200K and 300K is measured respectively, and result is as shown in Figure 3.With temperature
The raising of degree, spectral peak present raised trend after first reducing, this embody small organic molecule of the present invention have singlet and
Triplet state free radical and the structure deposited, ground state are triplet state, and the resonant structure of similar nitro stabilizes the series free radical.
(3) the ferromagnetism test of small molecule material 1:
Using the hysteresis loop of comprehensive physical property measuring system (Quantum Design PPMS) measurement sample.By 20mg sample
Product TPABT-OH is placed in the sample room under high vacuum state, passes through the cooling high temperature furnace option heating point with VSM on PPMS of liquid helium
Sample Yong Yu not tested under the conditions of temperature 20K, 100K, 200K and 350K.Test results are shown in figure 4 for it.Fig. 4 result table
Bright, non-linear relation is presented in the intensity of magnetization and external magnetic field of the organic small molecule material, still has under room temperature or even 350K high temperature
There is typical hysteresis loop, there is strong ferromagnetism.It can be used as the ferrimagnet haveing excellent performance.It can be applied to solution processing
Organic Iron magnetic device field.
Embodiment 2
According to the embodiment that 106397355 A of patent No. CN is announced, the small molecule material 2 of following structural formula is made
(TPATBT-OH):
The characterization of small molecule material 2:
5mg sample TPABT-OH is taken to be dissolved in deuterated dimethyl sulfoxide reagent, chemical shift passes through using TMS as internal standard
DRX-400MHz spectrometer (Bruker, Germany) records nucleus magnetic hydrogen spectrum peak at normal temperature.1H NMR(400MHz,DMSO)δ
9.40 (d, J=5.3Hz, 4H), 8.26 (s, 2H), 8.10-8.04 (m, 2H), 7.83 (d, J=7.7Hz, 1H), 7.25 (dd, J
=21.6,8.7Hz, 4H), 7.05-6.94 (m, 8H), 6.83-6.68 (m, 12H), 2.75-2.61 (m, 4H), 1.69-1.50
(m,5H),1.29–1.16(m,13H),0.87–0.79(m,7H)。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (2)
1. a kind of application of Organic micromolecular semiconductor material as organic ferromagnetic material, it is characterised in that the small organic molecule
Semiconductor material has general structure shown in formula (I):
A indicates the conjugation group with electron-withdrawing ability in formula.
2. a kind of application of the Organic micromolecular semiconductor material according to claim 1 as organic ferromagnetic material, special
Sign is: A has following described in any item structures in the formula (I):
Wherein R indicates alkyl.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705181A (en) * | 2019-01-24 | 2019-05-03 | 南开大学 | A kind of preparation method of derivative of macrolides |
| CN110283098A (en) * | 2019-07-10 | 2019-09-27 | 华南理工大学 | A kind of inorganic acid free radical semiconductor material of star-like aromatization and preparation and application |
| CN112266383A (en) * | 2020-11-16 | 2021-01-26 | 中国科学院合肥物质科学研究院 | Method for enhancing molecular planarity of non-spiral organic small molecule hole transport material |
| CN113173930A (en) * | 2021-03-09 | 2021-07-27 | 嘉兴学院 | Benzodithiophenedione-based non-doped hole transport material and synthesis method and application thereof |
| CN113402353A (en) * | 2021-05-12 | 2021-09-17 | 华南理工大学 | Preparation and application of lithium metal negative electrode based on aromatized nitric acid free radical modification |
| CN113912610A (en) * | 2021-09-15 | 2022-01-11 | 陕西理工大学 | Hydrogen bond association type undoped material, preparation method and application thereof, and perovskite solar cell |
| CN115124549A (en) * | 2022-07-08 | 2022-09-30 | 郑州大学 | Benzothienobenzothiophene organic magnetic compound, preparation method and application thereof |
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| CN102924402A (en) * | 2012-10-31 | 2013-02-13 | 中国科学院化学研究所 | 1,3,2-dithiazole free-radical conjugated molecule material and preparation method and application thereof |
| WO2016088793A1 (en) * | 2014-12-05 | 2016-06-09 | 日本化薬株式会社 | Organic compound and uses thereof |
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| WO2016088793A1 (en) * | 2014-12-05 | 2016-06-09 | 日本化薬株式会社 | Organic compound and uses thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705181A (en) * | 2019-01-24 | 2019-05-03 | 南开大学 | A kind of preparation method of derivative of macrolides |
| CN110283098A (en) * | 2019-07-10 | 2019-09-27 | 华南理工大学 | A kind of inorganic acid free radical semiconductor material of star-like aromatization and preparation and application |
| CN110283098B (en) * | 2019-07-10 | 2021-10-26 | 华南理工大学 | Star-shaped aromatized inorganic acid radical semiconductor material and preparation and application thereof |
| CN112266383A (en) * | 2020-11-16 | 2021-01-26 | 中国科学院合肥物质科学研究院 | Method for enhancing molecular planarity of non-spiral organic small molecule hole transport material |
| CN113173930A (en) * | 2021-03-09 | 2021-07-27 | 嘉兴学院 | Benzodithiophenedione-based non-doped hole transport material and synthesis method and application thereof |
| CN113173930B (en) * | 2021-03-09 | 2022-04-19 | 嘉兴学院 | Benzodithiophenedione-based non-doped hole transport material and synthesis method and application thereof |
| CN113402353A (en) * | 2021-05-12 | 2021-09-17 | 华南理工大学 | Preparation and application of lithium metal negative electrode based on aromatized nitric acid free radical modification |
| CN113912610A (en) * | 2021-09-15 | 2022-01-11 | 陕西理工大学 | Hydrogen bond association type undoped material, preparation method and application thereof, and perovskite solar cell |
| CN115124549A (en) * | 2022-07-08 | 2022-09-30 | 郑州大学 | Benzothienobenzothiophene organic magnetic compound, preparation method and application thereof |
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