CN106810570A - Green light type terbium (III) complex based on trans-aconitic acid part and preparation method thereof - Google Patents

Green light type terbium (III) complex based on trans-aconitic acid part and preparation method thereof Download PDF

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CN106810570A
CN106810570A CN201611169217.0A CN201611169217A CN106810570A CN 106810570 A CN106810570 A CN 106810570A CN 201611169217 A CN201611169217 A CN 201611169217A CN 106810570 A CN106810570 A CN 106810570A
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terbium
iii
fluorescent material
trans
crystalline state
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CN106810570B (en
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翟滨
李忠义
张付力
张弛
张向飞
曹广秀
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Shangqiu Normal University
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Shangqiu Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide

Abstract

Crystalline state terbium (III) fluorescent material the invention discloses a kind of green light based on trans-aconitic acid part and preparation method thereof, the molecular formula of the fluorescent material is [Tb (L) (DMF) (H2O)2]n(wherein, L3‑=trans-aconitic acid root anion, DMF=N, N dimethylformamides), mono-crystalline structures have two-dimensional layered structure, and its asymmetric construction unit includes trivalent terbium ion, trivalent trans-aconitic acid root part, a DMF molecule and two end water of coordination molecule.Synthesis of the invention and method of purification are simple, with low cost, and fluorescence property is good, have good application prospect in the field such as light emitting molecule device and fluorescence probe as fluorescent material.

Description

Green light type terbium (III) complex based on trans-aconitic acid part and preparation method thereof
Technical field
The invention belongs to optical material applied technical field, and in particular to a kind of green light based on trans-aconitic acid part Crystalline state terbium (III) fluorescent material：[Tb(L)(DMF)(H2O)2]n(wherein, L is trans-aconitic acid root anion, and DMF is N, N- Dimethylformamide), and preparation method thereof and its as fluorescent material in the field such as light emitting molecule device and fluorescence probe Using.
Background technology
With the fast development of inorganic porous material and synthesis chemistry, metal-organic framework material (Metal Organic Frameworks, MOFs) extensive concern is received in recent years as a kind of new porous material.Metal-organic framework material is not But with the porous crystal structure similar with traditional zeolite molecular screen material, and its structure also has Scalability and easy function The characteristic of change, has broad application prospects in fields such as catalysis, gas absorption, gas separation, optical materials. [Chem.Soc.Rev.,2008,37:191-214；Chem.Soc.Rev.,2009,38:1257-1283；Nature,2003, 423:705-714] rare earth ion has special electronic structure and bonding property because of it, can show the fluorescence of uniqueness Matter, and by the effect with part, its fluorescence intensity can be strengthened again, therefore the research of rare earth compounding is fluorescent material molecule Design provide wide prospect.Design and synthesis at present contains rare earth ion, especially Eu3+、Tb3+Metal complex, It is allowed to be one of the important topic in rare earth coordination chemical research field as light emitting molecule device and fluorescence probe. [Chem.Soc.Rev.,2009,38:1477-1504]
The content of the invention
The purpose of the present invention is intended to develop a kind of novel crystalline terbium (III) fluorescent material, while providing the preparation of this material Method and its as fluorescent material the field such as light emitting molecule device and fluorescence probe application.
To achieve the above object, the present invention uses following technical scheme：
A kind of crystalline state terbium (III) fluorescent material, the molecular formula of crystalline state terbium (III) fluorescent material is [Tb (L) (DMF) (H2O)2]n(wherein, L is trans-aconitic acid root, and DMF is DMF), the monocrystalline of crystalline state terbium (III) fluorescent material The asymmetric construction unit that structure has two-dimensional layered structure, described two-dimensional layered structure includes trivalent terbium ion, one Individual trivalent trans-aconitic acid root part, a DMF molecule and two end water of coordination molecule.
The preparation method of described crystalline state terbium (III) fluorescent material, step is as follows：By terbium nitrate, the water of trans-aconitic acid Solution is added in reaction bulb, is subsequently adding DMF, sodium hydrate aqueous solution is added dropwise under conditions of stirring, by the pH of system 2.2~3.0 are transferred to, are sealed after 5~10min of stirring, 20~48h is heated under 85~100 DEG C of constant temperature, be cooled to room Temperature, filtering, drying at room temperature obtain the terbium (III) fluorescent material.
The ratio between amount of material of the terbium nitrate and trans-aconitic acid is 1:2~20.
With 0.2mmol terbium nitrate benchmark, the consumption of the DMF is 2~10mL.
On the basis of 0.2mmol terbium nitrates, the concentration of the sodium hydrate aqueous solution is 0.1~2.0mol/L.
Described crystalline state terbium (III) fluorescent material is as luminescent material in light emitting molecule device and fluorescence probe field Using.
Beneficial effects of the present invention：The synthesis of crystalline state terbium (III) fluorescent material of the invention and method of purification are simple, condition Gently, with low cost, fluorescence property is good, the demand of industrial development can be met, as fluorescent material in light emitting molecule device The application prospect having had with the field such as fluorescence probe.
Brief description of the drawings
Fig. 1 is the coordination environment of asymmetric terbium ion in crystalline state terbium (III) fluorescent material mono-crystalline structures of the present invention.
Fig. 2 is the coordination mode of trans-aconitic acid part in crystalline state terbium (III) fluorescent material mono-crystalline structures of the present invention.
Fig. 3 is the two-dimensional layered structure of crystalline state terbium (III) fluorescent material mono-crystalline structures of the present invention.
Fig. 4 be crystalline state terbium (III) fluorescent material for preparing of embodiment 1 theory (under) and actual measurement (on) PXRD schemes.
Fig. 5 is the solid fluorescence launching light spectrogram of crystalline state terbium (III) fluorescent material that embodiment 1 is prepared.
Specific embodiment
For further explaination is of the invention, a series of embodiments are given below.These embodiments be entirely it is illustrative, they Only it is used for being specifically described the present invention, is not construed as limitation of the present invention.
Embodiment 1
The preparation method of crystalline state terbium (III) fluorescent material of the present embodiment is as follows：
By 200 microlitres of Tb (NO of 1mol/L3)3The aqueous solution and 2000 microlitres of trans-aconitic acids of 0.2mol/L it is water-soluble Liquid is placed in the bottle of 15mL, is subsequently adding 3mL DMF, in the case of stirring, is added dropwise over the NaOH water of 1mol/L PH is transferred to 2.5 by solution, and stirring is sealed after 10 minutes, is then placed on 90 DEG C of heated at constant temperature 24h in thermostatic drying chamber, is cooled to room Temperature, can obtain a large amount of clear crystals, filtering, wash three times, and drying at room temperature obtains crystalline state terbium (III) fluorescent material, and yield is 0.080g, yield is 91.1%.
(1) characterized as Bruker D8 ADVANCE powder x-ray diffractions crystal prototypes to obtained by, gained reality Survey and the peak of theoretical PXRD collection of illustrative plates be consistent (see accompanying drawing 4), and without miscellaneous peak appearance, it was demonstrated that obtained by crystalline state terbium (III) Fluorescent material purity is good, free from admixture.
(2) crystal data of crystalline state terbium (III) fluorescent material of the present embodiment
Its monocrystalline is detected by Bruker D8 Quest CMOS single crystal X-ray diffractions instrument, to the data obtained solution Analysis and refine can obtain：Molecular formula is C9H14TbNO9, molecular weight is 439.13, monoclinic system P21/cSpace group, cell parameterα=90 °, β=102.842 (2) °, γ=90 °, structure cell Volume V=1325.61 (12), density is 2.172g/cm3, Z=4.
(3) the solid fluorescence emission spectrum of crystalline state terbium (III) fluorescent material of the present embodiment
The solid fluorescence (see accompanying drawing 5) of gained crystalline state sample is have studied at room temperature.Gained complex has terbium ion Characteristic luminescence, has four narrow transmitting bands at 491,546,586 and 623nm, and this is attributable to Tb3+Ion5D4→7FJ (J=6,5,4,3) transition.Wherein peak intensity is most strong at 546nm, the green glow that complex is sent out strong.
Embodiment 2
The preparation method of crystalline state terbium (III) fluorescent material of the present embodiment, step is as follows
By 300 microlitres of Tb (NO of 1mol/L3)3The aqueous solution and 6000 microlitres of trans-aconitic acids of 0.2mol/L it is water-soluble Liquid is placed in the bottle of 15mL, is subsequently adding 6mL DMF, in the case of stirring, is added dropwise over the NaOH water of 2mol/L PH is transferred to 3.0 by solution, and stirring is sealed after 8 minutes, is then placed on 100 DEG C of heated at constant temperature 48h in thermostatic drying chamber, is cooled to room Temperature, filtering, drying at room temperature obtain the terbium (III) fluorescent material.
Embodiment 3
The preparation method of crystalline state terbium (III) fluorescent material of the present embodiment, step is as follows
By 100 microlitres of Tb (NO of 1mol/L3)3The aqueous solution and 5000 microlitres of trans-aconitic acids of 0.2mol/L it is water-soluble Liquid is placed in the bottle of 15mL, is subsequently adding 5mL DMF, in the case of stirring, is added dropwise over the NaOH water of 1mol/L PH is transferred to 2.8 by solution, and stirring is sealed after 5 minutes, is then placed on 95 DEG C of heated at constant temperature 24h in thermostatic drying chamber, is cooled to room Temperature, filtering, drying at room temperature obtain the terbium (III) fluorescent material.
Embodiment 4
The preparation method of crystalline state terbium (III) fluorescent material of the present embodiment, step is as follows
By 500 microlitres of Tb (NO of 1mol/L3)3The aqueous solution and 8000 microlitres of trans-aconitic acids of 0.2mol/L it is water-soluble Liquid is placed in the bottle of 30mL, is subsequently adding 12mL DMF, in the case of stirring, is added dropwise over the NaOH water of 2mol/L PH is transferred to 2.0 by solution, and stirring is sealed after 6 minutes, is then placed on 85 DEG C of heated at constant temperature 20h in thermostatic drying chamber, is cooled to room Temperature, filtering, drying at room temperature obtain the terbium (III) fluorescent material.
Embodiment 5
The preparation method of crystalline state terbium (III) fluorescent material of the present embodiment, step is as follows
By 50 microlitres of Tb (NO of 1mol/L3)3The aqueous solution and 5000 microlitres of aqueous solution of the trans-aconitic acid of 0.2mol/L It is placed in the bottle of 15mL, is subsequently adding 2.5mL DMF, in the case of stirring, is added dropwise over the NaOH of 0.1mol/L PH is transferred to 2.5 by the aqueous solution, and stirring is sealed after 10 minutes, is then placed on 90 DEG C of heated at constant temperature 30h in thermostatic drying chamber, is cooled to Room temperature, filtering, drying at room temperature obtain the terbium (III) fluorescent material.
General principle of the invention and principal character and advantages of the present invention has been shown and described above.The skill of the industry Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the simply explanation described in above-described embodiment and specification Principle of the invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and Its equivalent thereof.

Claims (6)

1. crystalline state terbium (III) fluorescent material of a kind of green light based on trans-aconitic acid part, it is characterised in that：The crystalline state The molecular formula of terbium (III) fluorescent material is [Tb (L) (DMF) (H2O)2]n(wherein, L is trans-aconitic acid root, and DMF is N, N- bis- NMF), the mono-crystalline structures of crystalline state terbium (III) fluorescent material have two-dimensional layered structure, described two-dimensional layered structure Asymmetric construction unit include a trivalent terbium ion, a trivalent trans-aconitic acid root part, a DMF molecule and two End water of coordination molecule.
2. the preparation method of crystalline state terbium (III) fluorescent material according to claim 1, it is characterised in that step is as follows：Will Terbium nitrate, the aqueous solution of trans-aconitic acid are added in reaction bulb, are subsequently adding DMF, and hydrogen-oxygen is added dropwise under conditions of stirring Change sodium water solution, the pH of system is transferred to 2.2 ~ 3.0, sealed after 5 ~ 10min of stirring, heated under 85 ~ 100 DEG C of constant temperature 20 ~ 48h, is cooled to room temperature, and filtering, drying at room temperature obtain the terbium (III) fluorescent material.
3. the preparation method of crystalline state terbium (III) fluorescent material according to claim 2, it is characterised in that：The terbium nitrate It is 1 with the ratio between the amount of material of trans-aconitic acid:2~20.
4. the preparation method of crystalline state terbium (III) fluorescent material according to claim 2, it is characterised in that：With 0.2mmol nitre Sour terbium benchmark, the consumption of the DMF is 2 ~ 10mL.
5. the preparation method of crystalline state terbium (III) fluorescent material according to claim 2, it is characterised in that：With 0.2mmol nitre On the basis of sour terbium, the concentration of the sodium hydrate aqueous solution is 0.1 ~ 2.0 mol/L.
6. crystalline state terbium (III) fluorescent material according to claim 1 as luminescent material in light emitting molecule device and fluorescence Application in probe field.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100286022A1 (en) * 2007-09-25 2010-11-11 The Regents Of The University Of California Edible and biocompatible metal-organic frameworks

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100286022A1 (en) * 2007-09-25 2010-11-11 The Regents Of The University Of California Edible and biocompatible metal-organic frameworks

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MING-SHENG WANG等: "Zinc complexes of T-shaped trans-1,2,3-propenetricarboxylic acid with 1-D ribbon-like chain, 2-D rhombus-grid-like and herringbone-like layers, and non-interpenetrating 3-D open framework", 《DALTON TRANS.》 *
XIAOJUN ZHAO等: "A Series of Three-Dimensional Lanthanide Coordination Compounds with the Rutile Topology", 《CRYSTAL GROWTH & DESIGN》 *

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