CN1300280C - Metallic organic complex with tribo-luminescent performance and its preparation process - Google Patents
Metallic organic complex with tribo-luminescent performance and its preparation process Download PDFInfo
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- CN1300280C CN1300280C CNB200510040058XA CN200510040058A CN1300280C CN 1300280 C CN1300280 C CN 1300280C CN B200510040058X A CNB200510040058X A CN B200510040058XA CN 200510040058 A CN200510040058 A CN 200510040058A CN 1300280 C CN1300280 C CN 1300280C
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- organic complex
- metal
- tribo
- thf
- luminescent performance
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Abstract
The present invention discloses a metal organic complex with triboluminescence performance, which is characterized in that the metal organic complex has a structural formula of (C12H8N) 2ZrCl2 (THF) 2, wherein THF is tetrahydrofuran. The present invention also relates to a preparation method of the metal organic complex, which comprises the steps: carbazole sodium salt and zirconium tetrachloride are respectively added to tetrahydrofuran organic solvent under the atmosphere of inert gas, and are stirred to make the carbazole sodium salt and the zirconium tetrachloride dissolve; reaction is carried out for at least 16 hours, and post-treatment is subsequently carried out to obtain the required metal organic complex. Strong green light can be visually observed when the product of the present invention is impacted under normal conditions.
Description
Technical field
The present invention relates to a kind of title complex that contains pentacyclic condensed heterocyclic compouds, especially a kind of have a tribo-luminescent performance contain a metal-organic complex of carbazole ligand and preparation method thereof.
Background technology
By causing its luminous phenomenon to be called as triboluminescence (Triboluminescence in some solid action of mechanical pressure, be abbreviated as TL), in broad terms, it is luminous also to can be described as machinery, in this process, this class solid material changes mechanical energy into luminous energy.Material with tribo-luminescent performance can be used for display element of making pressure-sensitive twinkler, pressure acquisition sensor and other scientific instrument etc.The history of TL is longer, as far back as eighties of last century, at G.E.Hardy, J.C.Baldwin, J.I.Zink, W.C.Kaska, P.-H.Liu, L.Duboisia, J.Am.Chem.Soc.1977,99,3552. in disclose several materials that contain aromatic group and had tribo-luminescent performance, they are luxuriant and rich with fragrance, acenaphthene, the phthalic acid acid anhydrides, (Ph
3PO)
2MnBr
2, (Ph
3PO)
2MnCl
2, [PhC (O)]
3P=P[C (O) Ph]
3, Eu[CH (COC
6H
5)
2]
4, 9-anthryl ethanol, acetyl anthranilic acid.They have good fluorescent characteristic simultaneously, but not all material with good fluorescence characteristic all has the excellent friction luminosity, has only some to contain specific ligand and fluorescent substance with specific crystalline structure just has the triboluminescence characteristic.Some attempt to excite air to explain and disclose triboluminescence mechanism from the angle of crystalline structure and friction, but scientific circles still do not have final conclusion to this so far.Generally believe to have that structure is non-centrosymmetrical accounting for more than 90% in the compound of tribo-luminescent performance at present.
Bibliographical information, the structure that the overwhelming majority has a metal-organic complex of tribo-luminescent performance all is non-centrosymmetrical.At F.A.Cotton, L.M.Daniels, P.Huang, Inorganic Chemistry2001 discloses six kinds of metal complexess with tribo-luminescent performance, (MePh in 40,3576.
3P)
2MnCl
4, (Et
4N)
2MnBr
4, (Ph
3PO)
2MnBr
2, (Ph
3PO)
2MnI
2, (Ph
3PO)
2MnCl
2(Ph
3AsO)
2MnBr
2, they all are the non-centrosymmetry structure.At F.A.Cotton, L.M.Daniels, P.Huang, Inorganic Chemistry Communications discloses the (NEt of non-centrosymmetry structure in 2001,4,319.
3H) { Eu[CH (COC
6H
5)
2]
4Also has a triboluminescent performance.At R.G.Xiong, X.Z.You, Inorganic Chemistry Communications discloses title complex (C in 2002,5,677.
6H
5CH
2NH) { Eu[CH (COC
6H
5)
2]
4Triboluminescent performance, its structure are also arranged also is non-centrosymmetrical.
Structure with tribo-luminescent performance is that centrosymmetric a metal-organic complex also has report.At A.L.Rheingold, W.King, Inorganic Chemistry discloses three kinds of a metal-organic complex Eu[CH (COC with tribo-luminescent performance in 1989,28,1715.
6H
5) (COCH
3)]
4(pip), six (phenopyrine) triiodide terbium and [Tb (H
2O)
6Cl
2] Cl, their structure all is centrosymmetric.At X.R.Zeng, R.G.Xiong, X.Z.You, K.K.Cheung, Inorganic ChemistryCommunications, disclosing a kind of structure in 2000,3,341. is centrosymmetric a metal-organic complex Eu[CH (COC with tribo-luminescent performance
6H
5)
2]
4(mor).
Thereby, can't whether symmetry judges that it has or not tribo-luminescent performance according to the fluorescent characteristic of compound or structure.Simultaneously, up to the present, also do not have the report of tribo-luminescent performance about the early transition metal organic coordination compound.Possess prospects for commercial application owing to have the material of tribo-luminescent performance, people are constantly seeking the new material with tribo-luminescent performance.
Summary of the invention
The object of the invention provides a kind of new a metal-organic complex with tribo-luminescent performance;
Another object of the present invention provides the preparation method of this a metal-organic complex.
For achieving the above object, the technical solution used in the present invention is: a kind of a metal-organic complex with tribo-luminescent performance, its structural formula are (C
12H
8N)
2ZrCl
2(THF)
2, wherein, THF is a tetrahydrofuran (THF).
For realizing another goal of the invention of the present invention, the technical scheme of employing is that a kind of preparation method with a metal-organic complex of tribo-luminescent performance under inert gas atmosphere, adds carbazole sodium salt (C respectively in the tetrahydrofuran (THF) organic solvent
12H
8NNa) and zirconium tetrachloride (ZrCl
4), stir and make it dissolving, reacted at least 16 hours, carry out aftertreatment again, obtain required a metal-organic complex.
In the technique scheme, carry out for making to react completely, the carbazole sodium salt of described adding and the mol ratio of zirconium tetrachloride are 2: 1.
Usually, reaction can at room temperature be carried out, but for fast reaction speed, also can suitably heat, and further technical scheme is that described temperature of reaction is between 20-80 ℃.
In the technique scheme, described aftertreatment is that the sodium-chlor of separating out by centrifugal removal is concentrated, freezing to mother liquor more earlier, obtains required a metal-organic complex.
In the preparation process of the present invention; what adopt is the system of the salt and the solvent composition of metal halide, organic ligand; under inert atmosphere, react; temperature of reaction is generally room temperature; wherein, described organic ligand is a containing n-donor ligand, and described solvent is not for containing the organic solvent of reactive hydrogen; reaction system must deoxygenation, dewater, with rare gas element (as argon gas or nitrogen) protection.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the metal halide that adopts in the preparation process of the present invention is a zirconium tetrachloride, and zirconium is a kind of early transition metal, constitute the triboluminescence material with early transition metal and do not appear in the newspapers at present, thereby the present invention has opened up a new road for seeking the triboluminescence material;
2. product of the present invention just can be estimated very strong green glow by bump under usual conditions.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
The reaction flask of band stirrer adds 0.2 mole carbazole sodium salt C under argon shield after deoxygenation, removing water treatment
12H
8NNa, 0.1 mole ZrCl
4, adding tetrahydrofuran (THF) as solvent, stirring is dissolved reactant fully, at room temperature reacts 24 hours.Reaction system is carried out centrifugal treating, remove the solid sodium chloride of separating out, concentrated, freezing to mother liquor again, promptly obtain (C
12H
8N)
2ZrCl
2(THF)
2, after measured, it is non-centrosymmetry structure [Crystal system:Orthorhombic; Space group:iba2].At room temperature clash into title complex (C
12H
8N)
2ZrCl
2(THF)
2Can estimate very strong green glow.
Claims (4)
1. a metal-organic complex with tribo-luminescent performance, it is characterized in that: its structural formula is (C
12H
8N)
2ZrCl
2(THF)
2, wherein, THF is a tetrahydrofuran (THF).
2. the described preparation method of claim 1 with a metal-organic complex of tribo-luminescent performance, it is characterized in that: under inert gas atmosphere, in the tetrahydrofuran (THF) organic solvent, add carbazole sodium salt and zirconium tetrachloride respectively, stirring makes it dissolving, reacts at least 16 hours, carries out aftertreatment again, described aftertreatment is, remove the sodium-chlor of separating out by centrifugal treating earlier, concentrated, freezing to mother liquor again, obtain required a metal-organic complex.
3. the preparation method of a metal-organic complex according to claim 2, it is characterized in that: the carbazole sodium salt of described adding and the mol ratio of zirconium tetrachloride are 2: 1.
4. the preparation method of a metal-organic complex according to claim 2, it is characterized in that: described temperature of reaction is between 20-80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510040058XA CN1300280C (en) | 2005-05-12 | 2005-05-12 | Metallic organic complex with tribo-luminescent performance and its preparation process |
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|---|---|---|---|
| CNB200510040058XA CN1300280C (en) | 2005-05-12 | 2005-05-12 | Metallic organic complex with tribo-luminescent performance and its preparation process |
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|---|---|
| CN1693414A CN1693414A (en) | 2005-11-09 |
| CN1300280C true CN1300280C (en) | 2007-02-14 |
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|---|---|---|---|
| CNB200510040058XA Expired - Fee Related CN1300280C (en) | 2005-05-12 | 2005-05-12 | Metallic organic complex with tribo-luminescent performance and its preparation process |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071010B (en) * | 2009-11-23 | 2014-03-05 | 中国科学院福建物质结构研究所 | Mechanical luminescent discoloration material of 5-acetylene-2,2'-platinum dipyridyl (II) compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071632A (en) * | 1995-01-06 | 2000-06-06 | Ciba Specialty Chemicals Corporation | Triboluminescent lanthanideIII complexes |
| CN1365381A (en) * | 2000-03-27 | 2002-08-21 | 出光兴产株式会社 | Organic electroluminescent element |
-
2005
- 2005-05-12 CN CNB200510040058XA patent/CN1300280C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071632A (en) * | 1995-01-06 | 2000-06-06 | Ciba Specialty Chemicals Corporation | Triboluminescent lanthanideIII complexes |
| CN1365381A (en) * | 2000-03-27 | 2002-08-21 | 出光兴产株式会社 | Organic electroluminescent element |
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| Publication number | Publication date |
|---|---|
| CN1693414A (en) | 2005-11-09 |
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