CN103435636A - Preparation method of long-persistence phosphorescent zinc complex having metal-organic framework material - Google Patents

Preparation method of long-persistence phosphorescent zinc complex having metal-organic framework material Download PDF

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Publication number
CN103435636A
CN103435636A CN201310422437XA CN201310422437A CN103435636A CN 103435636 A CN103435636 A CN 103435636A CN 201310422437X A CN201310422437X A CN 201310422437XA CN 201310422437 A CN201310422437 A CN 201310422437A CN 103435636 A CN103435636 A CN 103435636A
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metal
organic framework
preparation
long
persistence phosphorescent
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CN201310422437XA
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许文苑
罗峰
罗明标
刘淑娟
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East China Institute of Technology
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East China Institute of Technology
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Abstract

The invention relates to a preparation method of a long-persistence phosphorescent zinc complex having a metal-organic framework material, wherein the complex Zn(HCOO)2(L) having a metal-organic framework structure is obtained by complexing zinc nitrate, N,N'-bi-(4-pyridyl) phthalamide and benzoic acid in a mixed solvent of N,N'-dimethylformamide (DMF) and water. According to the preparation method of the long-persistence phosphorescent zinc complex having the metal-organic framework structure, disclosed by the invention, the novel long-persistence phosphorescent material having the metal-organic framework structure is obtained through simple solvent thermosynthesis; the novel long-persistence phosphorescent material has adjustability and composability; furthermore, the preparation method is simple; in addition, because of having a clear excited state equilibrium mechanism, the novel long-persistence phosphorescent material is convenient for adjustment of light emission and has a good long-persistence phosphorescent effect.

Description

Preparation method with steady persistence phosphorescent Zn complex of metal-organic framework materials
Technical field
The invention belongs to domain of inorganic chemistry, particularly a kind of preparation method with steady persistence phosphorescent Zn complex of metal-organic framework materials.
Background technology
Phosphorescence and twilight sunset, have another name called for steady persistence phosphorescence (LLPs), is that luminescence decay time can continue until second, minute after removing external light source and exciting, the luminescence process even arrived hour.This class material has important application in industry and daily life, as flat-panel monitor (PDP), photodiode (LED), fibre optic thermometer, emergency lighting, billboard, upholstery and dial plate etc.
At present, long-decay phosphor material is mainly sulfide, as ZnS:Cu, and oxide compound, as SrAl 2o 4: Dy, Eu, CaAl 2o 4: Nd, Eu, Sr 4al 14o 25: Dy, Eu.The detailed mechanism of LLPs is not yet clear at present, but generally believes it is the codopant effect.In addition, the concern in this field is also had to their thermostability, chemical stability, and simple synthetic route.Thus, scientific research person are devoted to the type material that LLPs is found in research, and metal-organic framework structured material (MOFs) has been opened the platform of its type material.Luminous MOFs material has the characteristic of tunable radiation emitting and the direct emission of white light, and this is to have three-dimensional structure adjustability and the composability of special metal-organic coordination, high-sequential due to it.Particularly, the MOFs material easily generates under gentle reaction conditions.These are just making the luminescent material of MOFs take advantage than traditional phosphor.That the luminescent lifetime of MOFs material reaches Millisecond is often rare earth MOFs, and other, as 3d metal M OFs, luminescent lifetime is generally microsecond or nanosecond.At present, there is the luminiferous MOFs material of continuing and not yet report, therefore there is very large researching value.
Summary of the invention
Purpose of the present invention just is to provide a kind of preparation method of easy to operate, stable, the strong steady persistence phosphorescent Zn complex with metal-organic framework materials of repeatability.
Preparation method with steady persistence phosphorescent Zn complex of metal-organic framework materials of the present invention, be in the time of 115 ℃, zinc nitrate, acid amides N, N-bis-(4-pyridyl) phthalamide( l) and phenylformic acid at N, in the mixed solvent of N '-dimethyl formamide (DMF) and water, reaction obtains a title complex Zn (HCOO) with metal-organic framework structure 2(L), concrete preparation method is:
By the 0.1mmol zinc nitrate, 0.1mmol N, N '-bis--(4-pyridyl) phthalamide and 0.2mmol phenylformic acid are put into the tetrafluoroethylene reactor, add 6ml N, N '-dimethyl formamide (DMF): the mixed solvent of water=5:1 is placed in muffle furnace, be heated to 110-120 ℃, constant temperature 40-50 hour, then with per hour 3 ℃ drop to room temperature, obtain target compound title complex Zn (HCOO) 2(L) the steady persistence phosphorescent Zn complex that, there is the metal-organic framework structure.
Preparation method with steady persistence phosphorescent Zn complex of metal-organic framework materials of the present invention, to synthesize and obtain a kind of novel long-decay phosphor material with metal-organic framework structure by simple solvent thermal, this material has controllability and composability, and the preparation method is simple, there is clear and definite excited state balancing, make luminous adjusting convenient, the steady persistence phosphorescent effect is good, the characteristics such as it is simple that this technology has technique, and repeatability is strong, and product performance are stable.
The accompanying drawing explanation
Fig. 1 is title complex Zn of the present invention (HCOO) 2(L) crystalline structure and topological diagram;
Fig. 2 is title complex Zn of the present invention (HCOO) 2(L) photoluminescence excitation and the spectrogram of emission;
Fig. 3 is title complex Zn of the present invention (HCOO) 2(L) afterglow intensity extinction curve figure;
Fig. 4 is the title complex Zn (HCOO) of invention 2(L) in different exciting under the time used, the afterglow intensity extinction curve figure at the 485nm place.
Embodiment
A kind of preparation method with steady persistence phosphorescent Zn complex of metal-organic framework materials, its concrete steps are, by the 0.1mmol zinc nitrate, 0.1mmol N, N '-bis--(4-pyridyl) phthalamide and 0.2mmol phenylformic acid are put into the tetrafluoroethylene reactor, add 6ml N, N '-dimethyl formamide (DMF): the mixed solvent of water=5:1, be placed in muffle furnace, be heated to 115 ℃, constant temperature 48 hours, then with per hour 3 ℃ drop to room temperature, obtain target compound title complex Zn (HCOO) 2(L) the steady persistence phosphorescent Zn complex that, there is the metal-organic framework structure.
This complex crystal is carried out to structural characterization and parsing, determine its structure cell and space structure.In addition, also it has been carried out to the Photoluminescence test, result shows: by regulating different excitation wavelengths, photoluminescence can be realized the adjusting from the blue light to the green glow; This compound has fluorescence and phosphorescent.For the Zn complex of most metal-organic framework structure, the photoluminescence luminescent lifetime that they have nanosecond, only have the phosphorescent that has individually the Microsecond grade luminescent lifetime.As can be seen here, title complex Zn (HCOO) 2(L) than other, the Zn complex of all metal-organic framework structures has superiority.At room temperature, after removing the excitation light source of UV-light, this title complex has shown that unprecedented macroscopic view continues luminescence phenomenon, and the estimated time length of naked eyes is about 1 second, and this phenomenon is very sensitive to excitation wavelength.Generally, the time length that external light source excites is to the long-persistence luminous property of inorganic materials very important (time length that external light source excites usually is longer, will produce longer persistence luminous).We are also to title complex Zn (HCOO) 2(L) test, structure shows: this title complex is not subject to the impact of this factor, means that the use of the steady persistence phosphorescent material with metal-organic framework structure is very easily.

Claims (1)

1. the preparation method with steady persistence phosphorescent Zn complex of metal-organic framework materials, it is characterized in that: its concrete steps are, by the 0.1mmol zinc nitrate, 0.1mmol N, N '-bis--(4-pyridyl) phthalamide and 0.2mmol phenylformic acid are put into the tetrafluoroethylene reactor, add 6ml N, N '-dimethyl formamide (DMF): the mixed solvent of water=5:1, be placed in muffle furnace, be heated to 110-120 ℃, constant temperature 40-50 hour, then with per hour 3 ℃ drop to room temperature, obtain target compound.
CN201310422437XA 2013-09-17 2013-09-17 Preparation method of long-persistence phosphorescent zinc complex having metal-organic framework material Pending CN103435636A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106833622A (en) * 2017-01-10 2017-06-13 南京工业大学 A kind of pure organic long-afterglow material of excited by visible light and preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1403533A (en) * 2001-08-31 2003-03-19 上海跃龙新材料股份有限公司 Long-decay phosphor material and its prepn
CN103242352A (en) * 2013-05-17 2013-08-14 聊城大学 Luminous metal-organic framework material with chemical sensing function as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1403533A (en) * 2001-08-31 2003-03-19 上海跃龙新材料股份有限公司 Long-decay phosphor material and its prepn
CN103242352A (en) * 2013-05-17 2013-08-14 聊城大学 Luminous metal-organic framework material with chemical sensing function as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FENG LUO ET AL.: "Promising long-lasting phosphor material: a novel metal-organic framework showing intriguing luminescent performance", 《THE ROYAL SOCIETY OF CHEMISTRY, DALTON TRANS. 》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106833622A (en) * 2017-01-10 2017-06-13 南京工业大学 A kind of pure organic long-afterglow material of excited by visible light and preparation method and application
CN106833622B (en) * 2017-01-10 2019-11-08 南京工业大学 A kind of pure organic long-afterglow material of excited by visible light and the preparation method and application thereof

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Application publication date: 20131211