CN103122243B - Platinum compound fluorescent material and preparation method thereof - Google Patents
Platinum compound fluorescent material and preparation method thereof Download PDFInfo
- Publication number
- CN103122243B CN103122243B CN201310033913.9A CN201310033913A CN103122243B CN 103122243 B CN103122243 B CN 103122243B CN 201310033913 A CN201310033913 A CN 201310033913A CN 103122243 B CN103122243 B CN 103122243B
- Authority
- CN
- China
- Prior art keywords
- fluorescent material
- compound
- acetylene
- platinum compound
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention discloses a platinum compound fluorescent material which is an acetylene pyridine platinum compound with a certain space structure. The molecular formula of the acetylene pyridine platinum compound is C50H38N2P2Pt; a crystal system is monoclinic; a space group is P21/c; unit cell parameters are as follows: a=12.0599Angstrom, b=22.474Angstrom, c=7.8012Angstrom, alpha=gamma=90 degrees, and beta=101.5980 degrees; and platinum ions are in a plane square coordination mode. The method disclosed by the invention can be used for preparing the acetylene pyridine platinum compound through chemical reaction by taking trans-coordination compound pt(pph3)2Cl2 and 4-acetylene pyridine hydrochloride as raw materials. The acetylene pyridine platinum compound has good photoelectric activity, shows good near-blue light emission property and film-forming property, can be used as a fluorescent material and a thin-film material and has potential application prospect.
Description
Technical field
The present invention relates to a kind of fluorescent material, especially relate to a kind of platinum compound fluorescent material and preparation method thereof.
Background technology
Fluorescence be material from excited state inactivation to the low-energy state that multiplicity is identical time the radiation that discharges.The energy that energy required when the most important condition that some compounds can produce fluorescence is chemical bond rupture the most weak in this compound molecule absorbs when there is the constant transition of multiplicity higher than it; Secondly, in its molecular structure will just like=C=O ,-N=O ,-N=N ,=C=S, the fluorophor such as=C=N-, when these groups are as molecular conjugation system a part of, this compound then may produce fluorescence.At present, fluorescent substance is widely used at numerous areas such as dyestuff, pigment dyestuff, optical whitening agent, photooxidant, coating, chemistry and biochemical analysis, sun power trap, anti-fake mark, pharmaceutical indications and laser.
Fluorescent material, typically refers to certain substance and the outside energy received is absorbed and store, and can be translated into a class material of luminous energy in the place of dark, is divided into inorganic fluorescent material and organic fluorescence materials.Inorganic fluorescent material be represented as rare earth luminescence and rare-earth luminescent material, most of rare earth element can be used to synthesizing inorganic fluorescent material, rare earth luminescent material plays a role in the fields such as display, illumination, photoelectric device as propping material, and have new fluorescent RE powder constantly to occur, as CRT fluorescent material, lamp phosphor, plasma flat-plate display (PDP) fluorescent material, long persistence luminescent powder, light-converting material, electroluminescent (EL) fluorescent material, Field emission displays (FED) uses fluorescent material.1963, beautiful Pope etc. observed the blue coloured electroluminous of anthracene, had pulled open and had obtained electroluminescent prelude with organic fluorescence materials; People utilize again fluorescent material to detect state and the change thereof of various different system afterwards.
Since earlier 1900s, organic fluorescence materials has been widely used in the aspects such as weaving, coloring plastic and printing color.Can roughly be divided into by material structure: the aromatic fused ring compound with rigid structure, the Intramolecular charge transfer with conjugated structure, some a metal-organic complex, the Intramolecular charge transfer wherein with conjugated structure is the class studying the most extensive and active at present, and is the luminophor that a class has good radiative decay ability.Many researchs in recent years show: the metal organic molecule of organic ligand containing conjugation primitive assembling with there is optically active metal ion compound can demonstrate good luminescent properties.In this type of research, organic composition and inorganic components can carry out autotelic screening to the size of metal ion or conjugation primitive, thus emission wavelength regulation; In addition, on a molecular scale, can the synthesis of designing material, be conducive to research material relation be-tween structure and properties like this and explore its luminescence mechanism, thus providing theoretical foundation for design advanced luminescent material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind ofly has platinum compound fluorescent material of good blue emission performance and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of platinum compound fluorescent material, and this fluorescent material is a kind of pyridinium acetylene platinic compound with certain space structure, and its molecular formula is C50H38N2P2Pt, and crystallographic system is monocline, and spacer is P2
1/
c, unit cell parameters
α=γ=90 °, β=101.5980 °, platinum ion is planar shape coordination mode.
A preparation method for platinum compound fluorescent material, comprises the following steps:
1) dimethyl formamide, methylene dichloride and diethylamine are formed mixed solvent with the volume ratio of 1:0.5 ~ 3:0.5 ~ 3, in this mixed solvent, then add trans title complex Pt (PPh
3)
2cl
2mixing solutions is formed, trans title complex Pt (PPh with 4-pyridinium acetylene hydrochloride
3)
2cl
2be 1:2 ~ 5 with the mol ratio of 4-pyridinium acetylene hydrochloride;
2) ratio with 5 ~ 20mol% in above-mentioned mixing solutions adds cuprous iodide, heating reflux reaction 6 ~ 24h;
3) after reaction terminates, cooling, produces light gray throw out, crosses and filters solvent, is used by the throw out obtained water, normal hexane, washed with diethylether for several times more successively, dry, obtains ash gray thick product;
4) thick product recrystallization in methylene dichloride and ether obtains colourless acicular crystal, and be described pyridinium acetylene platinic compound, after measured, the molecular formula of this pyridinium acetylene platinic compound is C
50h
38n
2p
2pt.
Document Acta.Cryst. (2000) .C56, e12-e15 disclose a kind of trans title complex Pt (PPh
3)
2cl
2preparation method, it is by triphenyl phosphorus (PPh
3) join containing cis and trans PtCl
2(SMe
2)
2in the acetone soln of mixture, stir, by cis title complex Pt (PPh
3)
2cl
2white depositions filtering separation from solution, then by cis title complex Pt (PPh
3)
2cl
2photochemistry isomerization reaction prepare trans title complex Pt (PPh
3)
2cl
2.
Preferably, in step 4), the volume ratio of methylene dichloride and ether is 1:1 ~ 10.
Preferably, the material of described participation reaction is chemical pure.
Compared with prior art, the invention has the advantages that: with trans title complex Pt (PPh
3)
2cl
2be that raw material carries out chemical reaction and obtains a kind of novel pyridinium acetylene platinic compound with 4-pyridinium acetylene hydrochloride, there is clear and definite space structure and molecular formula accurately, can be used as nearly blue light emitting material; Contain undersaturated carbon-to-carbon triple bond (alkynyl) in molecule, have and enrich optically active Pt (II) ion, pyridine atom N and the large π key of conjugation etc., be conducive to transition of electron and transmission ofenergy, thus pyridinium acetylene platinic compound of the present invention has good photoelectric activity, the alkynyl pyridine platinum compound fluorescent material of preparation has good nearly blue emission performance and film forming properties, has potential application prospect.
Accompanying drawing explanation
Fig. 1 is the space structure figure of pyridinium acetylene platinic compound of the present invention;
Fig. 2 is the fluorescence emission spectrogram of pyridinium acetylene platinic compound of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1:
5mL dimethyl formamide, 10mL methylene dichloride and 10mL diethylamine are mixed into mixed solvent, in this mixed solvent, then add 0.58g (i.e. 0.632mmol) trans title complex Pt (PPh
3)
2cl
2with 0.195g (i.e. 1.40mmol) 4-pyridinium acetylene hydrochloride, stir, form mixing solutions; The CuI of 12.38mg (i.e. 0.065mmol) is added as catalyzer, heating reflux reaction 10h under nitrogen protection in mixing solutions; After reaction terminates, cooling, the color of mixing solutions becomes redness or garnet from white, produces light gray throw out, crosses and filters solvent, is used by the throw out obtained water, normal hexane, washed with diethylether for several times more successively, dry, obtains ash gray thick product; Thick product recrystallization in the mixed solvent be made up of with the volume ratio of 1:1 methylene dichloride and ether obtains colourless acicular crystal, is described pyridinium acetylene platinic compound, and after measured, the molecular formula of this pyridinium acetylene platinic compound is C
50h
38n
2p
2pt.
Embodiment 2:
10mL dimethyl formamide, 15mL methylene dichloride and 18mL diethylamine are mixed into mixed solvent, in this mixed solvent, then add 1.17g (i.e. 1.264mmol) trans title complex Pt (PPh
3)
2cl
2with 0.433g (i.e. 3.10mmol) 4-pyridinium acetylene hydrochloride, stir, form mixing solutions; The CuI of 17.33mg (i.e. 0.091mmol) is added as catalyzer, heating reflux reaction 15h under nitrogen protection in mixing solutions; After reaction terminates, cooling, the color of mixing solutions becomes redness or garnet from white, produces light gray throw out, crosses and filters solvent, is used by the throw out obtained water, normal hexane, washed with diethylether for several times more successively, dry, obtains ash gray thick product; Thick product recrystallization in the mixed solvent be made up of with the volume ratio of 1:5 methylene dichloride and ether obtains colourless acicular crystal, is described pyridinium acetylene platinic compound, and after measured, the molecular formula of this pyridinium acetylene platinic compound is C
50h
38n
2p
2pt.
Embodiment 3:
5mL dimethyl formamide, 10mL methylene dichloride and 10mL diethylamine are mixed into mixed solvent, in this mixed solvent, then add 1.0g (i.e. 1.264mmol) trans title complex Pt (PPh
3)
2cl
2with 0.558g (i.e. 4.00mmol) 4-pyridinium acetylene hydrochloride, stir, form mixing solutions; The CuI of 0.036g (i.e. 0.19mmol) is added as catalyzer, heating reflux reaction 8h under nitrogen protection in mixing solutions; After reaction terminates, cooling, the color of mixing solutions becomes redness or garnet from white, produces light gray throw out, crosses and filters solvent, is used by the throw out obtained water, normal hexane, washed with diethylether for several times more successively, dry, obtains ash gray thick product; Thick product recrystallization in the mixed solvent be made up of with the volume ratio of 1:10 methylene dichloride and ether obtains colourless acicular crystal, is described pyridinium acetylene platinic compound, and after measured, the molecular formula of this pyridinium acetylene platinic compound is C
50h
38n
2p
2pt.
Embodiment 4:
5mL dimethyl formamide, 10mL methylene dichloride and 10mL diethylamine are mixed into mixed solvent, in this mixed solvent, then add 0.58g (i.e. 0.632mmol) trans title complex Pt (PPh
3)
2cl
2with 0.283g (i.e. 2.03mmol) 4-pyridinium acetylene hydrochloride, stir, form mixing solutions; The CuI of 15.62mg (i.e. 0.082mmol) is added as catalyzer, heating reflux reaction 8h under nitrogen protection in mixing solutions; After reaction terminates, cooling, the color of mixing solutions becomes redness or garnet from white, produces light gray throw out, crosses and filters solvent, is used by the throw out obtained water, normal hexane, washed with diethylether for several times more successively, dry, obtains ash gray thick product; Thick product recrystallization in the mixed solvent be made up of with the volume ratio of 1:8 methylene dichloride and ether obtains colourless acicular crystal, is described pyridinium acetylene platinic compound, and after measured, the molecular formula of this pyridinium acetylene platinic compound is C
50h
38n
2p
2pt.
Colourless acicular crystal obtained in above-described embodiment is measured.After measured, this colourless acicular crystal is pyridinium acetylene platinic compound, and its molecular formula is C
50h
38n
2p
2pt, its space structure figure as shown in Figure 1.
Carry out fluorescence property test to colourless acicular crystal obtained in above-described embodiment, as shown in the fluorescence emission spectrogram of Fig. 2, this pyridinium acetylene platinic compound demonstrates good nearly blue emission performance, and has good film forming properties.
Claims (4)
1. a platinum compound fluorescent material, it is characterized in that this fluorescent material is a kind of pyridinium acetylene platinic compound with certain space structure, its molecular formula is C
50h
38n
2p
2pt, crystallographic system is monocline, and spacer is P2
1/ c, unit cell parameters
α=γ=90 °, β=101.5980 °, platinum ion is planar shape coordination mode.
2. a preparation method for platinum compound fluorescent material, is characterized in that comprising the following steps:
1) dimethyl formamide, methylene dichloride and diethylamine are formed mixed solvent with the volume ratio of 1:0.5 ~ 3:0.5 ~ 3, in this mixed solvent, then add trans title complex Pt (PPh
3)
2cl
2mixing solutions is formed, trans title complex Pt (PPh with 4-pyridinium acetylene hydrochloride
3)
2cl
2be 1:2 ~ 5 with the mol ratio of 4-pyridinium acetylene hydrochloride;
2) ratio with 5 ~ 20mol% in above-mentioned mixing solutions adds cuprous iodide, heating reflux reaction 6 ~ 24h;
3) after reaction terminates, cooling, produces light gray throw out, crosses and filters solvent, is used by the throw out obtained water, normal hexane, washed with diethylether for several times more successively, dry, obtains ash gray thick product;
4) thick product recrystallization in methylene dichloride and ether obtains colourless acicular crystal, and be described pyridinium acetylene platinic compound, after measured, the molecular formula of this pyridinium acetylene platinic compound is C
50h
38n
2p
2pt.
3. preparation method according to claim 2, is characterized in that in step 4), and the volume ratio of methylene dichloride and ether is 1:1 ~ 10.
4. the preparation method according to Claims 2 or 3, is characterized in that the material of described participation reaction is chemical pure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310033913.9A CN103122243B (en) | 2013-01-28 | 2013-01-28 | Platinum compound fluorescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310033913.9A CN103122243B (en) | 2013-01-28 | 2013-01-28 | Platinum compound fluorescent material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103122243A CN103122243A (en) | 2013-05-29 |
| CN103122243B true CN103122243B (en) | 2015-01-28 |
Family
ID=48453395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310033913.9A Expired - Fee Related CN103122243B (en) | 2013-01-28 | 2013-01-28 | Platinum compound fluorescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103122243B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19943102A1 (en) * | 1999-09-09 | 2001-03-15 | Wacker Chemie Gmbh | Preparation of bis(alkynyl)bis(phosphano)platinum complex, useful as e.g. cure catalyst for organopolysiloxane elastomer, involves reacting bis(phosphano)platinum dihalide and alkyne in presence of amine, alcohol and copper(I) iodide |
| US6359098B1 (en) * | 1999-08-13 | 2002-03-19 | Wacker-Chemie Gmbh | Curable organopolysiloxane materials |
| US7355057B1 (en) * | 2004-11-17 | 2008-04-08 | Cooper Thomas M | Liquid transition metal acetylide chromophores |
| CN102191039A (en) * | 2010-03-17 | 2011-09-21 | 宁波大学 | Platinum compound fluorescent material and preparation method thereof |
-
2013
- 2013-01-28 CN CN201310033913.9A patent/CN103122243B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6359098B1 (en) * | 1999-08-13 | 2002-03-19 | Wacker-Chemie Gmbh | Curable organopolysiloxane materials |
| DE19943102A1 (en) * | 1999-09-09 | 2001-03-15 | Wacker Chemie Gmbh | Preparation of bis(alkynyl)bis(phosphano)platinum complex, useful as e.g. cure catalyst for organopolysiloxane elastomer, involves reacting bis(phosphano)platinum dihalide and alkyne in presence of amine, alcohol and copper(I) iodide |
| US7355057B1 (en) * | 2004-11-17 | 2008-04-08 | Cooper Thomas M | Liquid transition metal acetylide chromophores |
| CN102191039A (en) * | 2010-03-17 | 2011-09-21 | 宁波大学 | Platinum compound fluorescent material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103122243A (en) | 2013-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102876320B (en) | Cuprous complex luminescent material and preparation method thereof | |
| CN104140808B (en) | A kind of cuprous complex luminescent material of tetrahedral of Han oxazolyl pyridine ligand | |
| CN102899029B (en) | Luminescent material of cuprous iodide complex and preparation method thereof | |
| CN103588794A (en) | Cuprous complex luminescence material and preparation method thereof | |
| CN102876319B (en) | Spirofluorene pyridine fluorescent material and preparation method thereof | |
| CN104927842A (en) | CuIN2P-type red light emitting material with cuprous complexes | |
| CN103242298A (en) | 1,2,4-triazole derivative, preparation method and application thereof and organic electroluminescent device | |
| CN110183475A (en) | Double boron oxa- pyrene compounds and its application based on donor-receiver | |
| CN104152140B (en) | A kind of blue fluorescent material and preparation method thereof | |
| CN104861962B (en) | A kind of Cu4I4 class cubane bunch core complex luminescent material based on Phosphine ligands | |
| CN104893715B (en) | Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core | |
| CN104961770A (en) | Pyronyl phosphine ligand based cuprous-complex green phosphorescent material | |
| CN104178131A (en) | Mixed cuprous complex luminescent material containing oxazolyl pyridine ligand | |
| Wu et al. | Dual emission from donor-modified MR-TADF emitter: Evidence for coexistence of TICT and MR excited states | |
| CN102719237B (en) | Zn(II) complex luminescent material and its preparation method | |
| CN103122243B (en) | Platinum compound fluorescent material and preparation method thereof | |
| CN104910897A (en) | Cu3I2 cationic cuprous cluster compound green phosphor material | |
| CN104892645A (en) | Cuprous complex phosphor material of methyl substitution benzoxazolyl pyridine | |
| CN102585800B (en) | Fluorine pyridine fluorescent material and preparation method thereof | |
| CN104861961A (en) | CuIN2P tetrahedral coordination cuprous complex luminous material | |
| CN103936777B (en) | The application of the bidentate aromatic phosphines oxygen europium complex modified with diethyl fluorene group | |
| CN103113185A (en) | Fluorobenzofiurene organic fluorescent material and preparation method thereof | |
| CN104830321B (en) | A kind of three-fold coordination type double-core Hydro-Giene (Water Science). complex luminescent material | |
| Huang et al. | Three-component color-tunable room temperature afterglow doped materials through Förster-resonance energy transfer | |
| CN105153230A (en) | Azafluorene and phosphine blended tricoordinated copper iodide complex luminescent material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150128 Termination date: 20180128 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |