CN100338173C - Metallic organic complex with tribo-luminescent performance and preparation process thereof - Google Patents
Metallic organic complex with tribo-luminescent performance and preparation process thereof Download PDFInfo
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- CN100338173C CN100338173C CN 200510040057 CN200510040057A CN100338173C CN 100338173 C CN100338173 C CN 100338173C CN 200510040057 CN200510040057 CN 200510040057 CN 200510040057 A CN200510040057 A CN 200510040057A CN 100338173 C CN100338173 C CN 100338173C
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- npr
- organic complex
- metal
- tribo
- luminescent performance
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Abstract
The present invention discloses a metal organic complex which has triboluminescence performance. The metal organic complex has a structural formula of [Pr<i>NC (NPr2<i>)NPr<i>]2ZrCl2, wherein Pr<i> is isopropyl. The present invention also relates to a preparation method that [Pr<i>NC (NPr2<i>)NPr<i>]Li and ZrCl4 are respectively added to organic solvent and stirred to make the [Pr<i>NC (NPr2<i>)NPr<i>]Li and the ZrCl4 dissolve under inert gas atmosphere, reaction is carried out for at least 16 hours, and post-processing is then carried out to obtain the required metal organic complex. As long as the product of the present invention is impacted under normal conditions, strong green light can be visually observed.
Description
Technical field
The present invention relates to a kind of title complex of guanidine, especially a kind of a metal-organic complex that contains the guanidine part and preparation method thereof with tribo-luminescent performance.
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)
6C1
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 [Pr
iNC (NPr
i 2) NPr
i]
2ZrCl
2, wherein, Pr
iBe sec.-propyl.
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 [Pr respectively in organic solvent
iNC (NPr
i 2) NPr
i] Li and 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 [the Pr of described adding for making to react completely
iNC (NPr
i 2) NPr
i] Li and ZrCl
4Mol ratio be 2: 1.
Difference according to organic solvent, because the solvability difference of reaction product, the aftertreatment of being carried out also has difference, when described organic solvent is tetrahydrofuran (THF), described aftertreatment is that elder generation drains reaction system, adds the toluene dissolving again, the undissolved lithium chloride of centrifugal removal, concentrated, freezing to mother liquor again.
When described organic solvent was selected from toluene or ether, described aftertreatment was, the lithium chloride solid that centrifugal removal is separated out, again to mother liquor concentrate, freezing.
Usually, reaction can at room temperature be carried out, but for fast reaction speed, also can suitably heat, further technical scheme, and described temperature of reaction is between 20-80 ℃.
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;
3. the nitrogenous organic ligand of organic ligand of the present invention for being widely used in other field, a metal-organic complex of acquisition is a metal-organic complex that contains metal nitrogen key, raw material obtains comparatively convenient.
Description of drawings
Accompanying drawing 1 is a metal-organic complex triboluminescence spectrogram at room temperature that the embodiment of the invention one obtains:
Accompanying drawing 2 is the emmission spectrum figure of a metal-organic complex of embodiment one.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one:
The reaction flask of band stirrer adds 0.2 mole [Pr under argon shield after deoxygenation, removing water treatment
iNC (NPr
i 2) NPr
i] Li, 0.1 mole ZrCl
4, adding tetrahydrofuran (THF) as solvent, stirring is dissolved reactant fully, at room temperature reacts 24 hours; Earlier reaction system is drained, added the toluene dissolving again, the undissolved lithium chloride of centrifugal removal, concentrated, freezing to mother liquor again, the product that obtains is [Pr
iNC (NPr
i 2) NPr
i]
2ZrCl
2, after measured, it is non-centrosymmetry structure [Crystal system:Monoclinic; Space group:Pc].At room temperature clash into title complex [Pr
iNC (NPr
i 2) NPr
i]
2ZrCl
2Test its triboluminescence emmission spectrum.Spectrogram according to test simulates its triboluminescence emmission spectrum figure shown in dotted line in the accompanying drawing 1, and the optimum transmit wavelength is about 480nm, and the emmission spectrum figure of title complex under solid-state, normal temperature is closely similar in its curve shape and the accompanying drawing 2.
Embodiment two:
The reaction flask of band stirrer adds 0.2 mole [Pr under argon shield after deoxygenation, removing water treatment
iNC (NPr
i 2) NPr
i] Li, 0.1 mole ZrCl
4, adding toluene as solvent, stirring is dissolved reactant fully, at room temperature reacts 24 hours; The lithium chloride solid that centrifugal removal is separated out, concentrated, freezing to mother liquor again, the product that obtains is [Pr
iNC (NPr
i 2) NPr
i]
2ZrCl
2
Claims (4)
1. a metal-organic complex with tribo-luminescent performance, it is characterized in that: its structural formula is [Pr
iNC (NPr
i 2) NPr
i]
2ZrCl
2, wherein, Pr
iBe sec.-propyl.
2. the described preparation method with a metal-organic complex of tribo-luminescent performance of claim 1 is characterized in that: under inert gas atmosphere, add [Pr respectively in organic solvent
iNC (NPr
i 2) NPr
i] Li and ZrCl
4, stir and make it dissolving, reacted at least 16 hours, carry out aftertreatment again, obtain required a metal-organic complex, wherein, described aftertreatment is selected one of following method according to the organic solvent that uses,
When described organic solvent was tetrahydrofuran (THF), described aftertreatment was, earlier reaction system drained, and added the toluene dissolving again, the undissolved lithium chloride of centrifugal removal, again to mother liquor concentrate, freezing;
When described organic solvent was selected from toluene or ether, described aftertreatment was, the lithium chloride solid that centrifugal removal is separated out, again to mother liquor concentrate, freezing.
3. the preparation method of a metal-organic complex according to claim 2 is characterized in that: [the Pr of described adding
iNC (NPr
i 2) NPr
i] Li and ZrCl
4Mol ratio be 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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| CN 200510040057 CN100338173C (en) | 2005-05-12 | 2005-05-12 | Metallic organic complex with tribo-luminescent performance and preparation process thereof |
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|---|---|
| CN1693413A CN1693413A (en) | 2005-11-09 |
| CN100338173C true CN100338173C (en) | 2007-09-19 |
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| 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 |
| CN106008563A (en) * | 2016-05-23 | 2016-10-12 | 北京百灵威科技有限公司 | Method for removing solid impurities in organic metal reagent solution |
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