CN105440064B - Rare earth complex and preparation method thereof - Google Patents

Rare earth complex and preparation method thereof Download PDF

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Publication number
CN105440064B
CN105440064B CN201510882090.6A CN201510882090A CN105440064B CN 105440064 B CN105440064 B CN 105440064B CN 201510882090 A CN201510882090 A CN 201510882090A CN 105440064 B CN105440064 B CN 105440064B
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rare earth
solution
preparation
volatilization
earth compound
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CN105440064A (en
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曾承辉
陶蓬
赵志鹏
李莎莎
李丹
钟声亮
李苑
王雷
丁立稳
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Jiangxi 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
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)

Abstract

The invention relates to a rare earth complex which is prepared through a volatilization method and of which the fluorescence quantum yield is larger than 60% and a preparation method thereof. The preparation method comprises the following steps that 1, LnmXn is dissolved in a solution for standby application; 2, a deprotonated 3-chloro-2,4-difluorobenzoic acid solution is added into the solution obtained in the step 1; 3, the mixed solution is placed for volatilization or heated for volatilization, and the phenomenon that powder or crystals is/are separated out can be seen after a period of time; 4, the powder or crystals obtained in the last step is/are filtered and air-dried. The method is simple and easy to operate, reasonable in design and suitable for various kinds of metal ions and ligands, the method for preparing the rare earth complex crystals is simple and convenient, valuable instruments and equipment are not needed, and the very high creativity is achieved.

Description

Rare earth compounding and preparation method thereof
Technical field
The present invention relates to high-fluorescence quantum yield rare earth complex compoud preparing technical field, and in particular to utilize volatility process Prepare the preparation method of rare earth compounding of the fluorescence quantum yield more than 60%.
Background technology
Rare earth element has 17, the 15 kinds of elements of lutecium (Lu) comprising the lanthanum (La) from atomic number 57 to 71, plus upper In the scandium (Sc) that the atomic number of same III B races is 21 and yttrium (Y) that atomic number is 39.Rare earth element outer electronic structure phase Together, the 4f electron energy levels of internal layer are close, make the coordination compound containing rare earth element show the physics and chemical property of many uniquenesses, example Such as：The properties such as high coordinating, luminescence generated by light, photoelectric conversion, magnetic, thus have in fields such as catalysis, light, electricity, magnetic extensive Using；Coordination compound be metal ion with organic ligand by the bonded formation of coordination it is highly regular, repeat to tie with certain The compound of structure unit, design and the synthesis of coordination compound are the important contents of Coordinative Chemistry research.To improve sending out for rare earth ion Light intensity, people are frequently with the organic ligand containing conjugation group and Ln3+Ion coordination forms rare earth compounding, such part Specific absorbance is big, and the energy efficient of absorption can be passed to into Ln3+, so as to be sensitized rare earth ion, significantly improve Ln3+Ion Luminous intensity.
Rare earth compounding has unique photoluminescent property, such as：It is the fluorescence lifetime of long Millisecond, narrow emission, larger Stokes displacements, light-emitting zone throughout visible region such as：Sm3+、Eu3+、Tb3+、Dy3+Transmitting and near infrared region such as：Nd3+、Er3 +、Yb3+Transmitting.Functional group in part, and with the O-H, N-H and the C-H that contain in the molecular/ionic of rare-earth ion coordination Some luminous processes of rare earth compounding Rare Earth Ion or stage can be affected, for example：Energy is affected from part to rare earth ion Transmission, affect the environment of coordination compound Rare Earth Ion, affect the vibration of coordinating group, affect light absorbs etc. of part, so as to Change the properties such as fluorescence quantum yield, the fluorescence lifetime of rare earth ion.Using the change of these photoluminescent properties, just synthesis can be designed Go out the rare earth compounding of high-fluorescence quantum yield.
The outer-shell electron of rare earth ion is in f orbitals, and luminous efficiency is very low when directly exciting, so needing with conjugated radicle The part of group, as " antenna ", can just effectively absorb the energy of photon and produce effective fluorescence and send out with rare-earth ion coordination Penetrate.Based on this, scientists have been done some and have been explored and significant work in terms of synthesis high-fluorescence quantum yield rare earth compounding Make.As Parker professor report on Angew.Chem.Int.Edit. within 2014 one in water fluorescence quantum yield reach 28% rare earth compounding；Professor Mazzanti is high using the rare earth compounding fluorescence quantum yield of acetylacetone,2,4-pentanedione derivant synthesis Up to 70%；The fluorescence quantum yield in dilution heat of sulfuric acid is high using the rare earth compounding of three nitrogen heterocycles parts synthesis for professor Ogo Up to 50%, and fluorescence quantum yield brings up to 90% in nitrogen atmosphere；Pecoraro teaches 2014 in the dilute of JACS reports Native coordination compound near-infrared fluorescent quantum yield can reach 3.8%；Yan Chunhua teaches the rare earth for being published in Nat.Commun. for 2014 Conversion efficiency is up to 16% on compound fluorescence.Applicant also reported one in 2014 by adjusting ligand solvent molecule, Terbium (III) complex fluorescent quantum yield is made from 4% mutation to 46%, but, close with luminous organic material 100% fluorescence Quantum yield is compared, the fluorescence quantum yield of rare earth compounding or low, and this exactly rare earth compounding illumination field is urgently solved A difficult problem certainly.
The content of the invention
The technical problem to be solved is to provide the rare earth compounding with high-fluorescence quantum yield and its preparation Method.
To solve above-mentioned technical problem, the present invention provides technical scheme below：
Rare earth compounding in the present invention is the chloro- 2,4 difluorobenzene formic acid of part 3- and 2 by rare earth element, 2 ' bipyridyls The coordination compound constructed, the rare earth element includes：Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、 At least one in Lu.
The preparation method of middle rare earth coordination compound of the present invention comprises the steps：A) by LnmXnBe dissolved in it is standby in solution, on Ln is rare earth ion in examination, and X is anion, and m and n is natural number；
B) by the chloro- 2,4 difluorobenzene formic acid solutions of the 3- of deprotonation, and 2,2 ' bipyridyl solutions are added in step a) In solution；
C) solution mixed above is placed into volatilization or heats volatilization, can see thering is powder or monocrystalline analysis after a period of time Go out；
D) powder obtained in the previous step or monocrystalline are filtered and is dried.
Rare earth compounding in the present invention can also be prepared by another approach, specifically prepare approach as follows：1) will The chloro- 2,4 difluorobenzene formic acid solution deprotonations of 3-, add 2,2 ' bipyridyl solution mix homogeneously；
2) by LnmXnIn being dissolved in solution, Ln in above-mentioned examinationm=rare earth ion, X=aniones, m and n is natural number；
3) will be by step 1) solution that obtains and step 2) obtained in solution mix homogeneously, mixed solution place volatilization or Heating volatilization, can see after a period of time has powder or monocrystalline to separate out；
4) powder obtained in the previous step or crystal are filtered, is dried, that is, it is higher than 60% to have obtained fluorescence quantum yield Tb coordination compounds.
The step c) and step 3) in the volatilization environment of mixed solution include in an atmosphere and in other gaseous environments In, and rare earth compounding is obtained by volatilization removal solvent.
Dissolving LnmXn, the solvent of 2,2 ' bipyridyls and the chloro- 2,4 difluorobenzene formic acid of 3- is water or/and organic solvent.
Preferably, the organic solvent be dimethyl sulfoxide, DMF, tetrahydrofuran, methanol, ethanol, Acetone, acetonitrile, at least one in dichloromethane and chloroform.
The present invention has an advantageous effect in that compared with prior art：Wherein, the present invention is with the chloro- 2,4 difluorobenzene first of 3- Acid, 2,2 ' bipyridyls and rare earth metal salt are raw material, are prepared for the rare earth with high-fluorescence quantum yield using volatility process and coordinate Thing monocrystalline, its absolute fluorescence quantum yield is higher than 60%；Wherein, middle rare earth complex crystal of the present invention prepare it is different from the past Either physically or chemically, it is to contain O-H, the less part of N-H and C-H agitators by employing, and can squeeze out moisture The bipyridyl of assistant ligand 2,2 ' and rare-earth salts placing response of son coordination, by volatility process crystal is grown, and the method is simple, Modern design is rationally, it is adaptable to all kinds of metal ions and part, and prepares the method simplicity of rare earth compounding monocrystalline, without the need for valuable Instrument and equipment.
Description of the drawings
The structural representation of the rare earth compounding that Fig. 1 is synthesized with rare earth Tb；
The atom of Fig. 2 and Tb coordinations arrangement figure in the way of the two cap triangular prisms for distorting；
The coordination mode figure of Fig. 3 parts and Tb；
The fluorescence decay figure of the Tb coordination compounds of Fig. 4 synthesis；
The laser and launching light spectrogram of the Tb coordination compounds of Fig. 5 synthesis.
Specific embodiment
With reference to embodiment, the present invention is described further, but is not limited to following embodiments.
Embodiment 1, the preparation of Tb coordination compounds and its crystal structure.
(1) the chloro- 2,4 difluorobenzene formic acid of 11.0mg 3- is placed in beaker, adds 1ml water, and use sodium hydroxide solution It is 6 to adjust pH, obtains solution A；
(2) by 8.7mg Tb (NO3)3·6H2O mixes with the bipyridyls of 2.9mg 2,2 ', adds the dissolving of 2ml acetylacetone,2,4-pentanediones, obtains Solution B；
(3) solution A and solution B are mixed, gained mixed liquor volatilizees in room temperature, obtains the new rare earth compound of clear crystal I。
Ray crystallographic analysis show new rare earth compound I for anorthic system, new rare earth compound I P-1 space groups 11.1669 (8), b=11.2383 (8), Z=1, its point Minor is Tb2C62H32Cl8F14N4O14, new rare earth compound I is the molecule of double-core, and adjacent dual-core architecture is connected by hydrogen bond Come, be built into the supramolecular network structure of three-dimensional.As can be seen from Figure 4 the excitation wavelength of new rare earth compound I is 318nm, There is obvious fluorescence emission peak at 489nm, 545nm, 585nm, 621nm, as can be seen from Figure 4 rare earth compound I's is glimmering The light life-span is 1.0ms.
Embodiment 2, the preparation of new rare earth compounding II.
(1) the chloro- 2,4 difluorobenzene formic acid of 10.0mg 3- is placed in beaker, adds 2ml water, and use sodium hydroxide solution It is 5 to adjust pH, obtains solution C；
(2) by 7.8mg Tb (NO3)3·6H2O mixes with the bipyridyls of 2.0mg 2,2 ', adds the dissolving of 2ml acetylacetone,2,4-pentanediones, obtains Solution D；
(3) solution C and solution D are mixed, gained mixed liquor volatilizees in room temperature, obtains the new rare earth compound of clear crystal II。
Confirm that it is same with the new rare earth compound I in embodiment 1 by analyzing the crystal structure of new rare earth compound II One material.
Embodiment 3, the preparation of new rare earth compounding III and its crystal structure.
(1) the chloro- 2,4 difluorobenzene formic acid of 12.0mg 3- is placed in beaker, adds 2ml water, and use sodium hydroxide solution It is 5 to adjust pH, obtains solution E；
(2) by 6.0mg Gd (NO3)3With the mixing of the bipyridyls of 3.0mg 2,2 ', the dissolving of 3ml acetylacetone,2,4-pentanediones is added, obtain solution F；
(3) solution E and solution F are mixed, gained mixed liquor volatilizees in room temperature, obtains the new rare earth compound of clear crystal III。
Ray crystallographic analysis show new rare earth compound III for anorthic system, new rare earth compound The P-1 space groups 11.1672 (8) of III, b=11.2201 (8), Z=1, Its molecular formula is Gd2C62H32Cl8F14N4O14, new rare earth compound III is the molecule of double-core, and adjacent dual-core architecture passes through hydrogen bond Couple together, be built into the supramolecular network structure of three-dimensional.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (1)

1. a kind of preparation method of Tb rare earth compoundings, it is characterised in that comprise the steps：
(1) the chloro- 2,4 difluorobenzene formic acid of 11.0mg 3- is placed in beaker, adds 1ml water, and adjusted with sodium hydroxide solution PH is 6, obtains solution A；
(2) by 8.7mg Tb (NO3)3·6H2O mixes with the bipyridyls of 2.9mg 2,2 ', adds the dissolving of 2ml acetylacetone,2,4-pentanediones, obtains solution B；
(3) solution A and solution B are mixed, gained mixed liquor volatilizees in room temperature, obtains the new rare earth compound I of clear crystal；It is single The new rare earth compound I of crystal structure analysis shows is anorthic system, and new rare earth compound I belongs to P-1 space groups, a=11.1669 (8), b=11.2383 (8), α=72.9760 (10) °, β=69.4420 (10) °, γ= 67.6760 (10) °,Z=1, its molecular formula is Tb2C62H32Cl8F14N4O14, new rare earth compound I is The molecule of double-core, adjacent dual-core architecture is coupled together by hydrogen bond, is built into the supramolecular network structure of three-dimensional.
CN201510882090.6A 2015-12-03 2015-12-03 Rare earth complex and preparation method thereof Expired - Fee Related CN105440064B (en)

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CN107286350B (en) * 2017-06-28 2021-06-15 江西师范大学 Rare earth coordination polymer with high thermal stability and preparation method thereof
CN107312027A (en) * 2017-06-28 2017-11-03 江西师范大学 The method for the crystalline material that one pot process organic matter containing cystine linkage and the cluster compound of rare earth containing cystine linkage coexist under normal temperature
CN107383385A (en) * 2017-08-02 2017-11-24 金华职业技术学院 A kind of 2 iodo-benzoic acid double-core lanthanum (III) complexs and preparation method thereof
CN113880868B (en) * 2021-10-12 2023-09-08 江西师范大学 Binuclear rare earth complex crystalline material and preparation method and application thereof
CN113999111B (en) * 2021-11-22 2024-04-09 包头稀土研究院 Chiral organic rare earth complex and preparation method and application thereof

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