CN105017294A - Thiadiazole dicarboxylic acid terbium coordination compound, preparation method and applications thereof - Google Patents

Thiadiazole dicarboxylic acid terbium coordination compound, preparation method and applications thereof Download PDF

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CN105017294A
CN105017294A CN201510335431.8A CN201510335431A CN105017294A CN 105017294 A CN105017294 A CN 105017294A CN 201510335431 A CN201510335431 A CN 201510335431A CN 105017294 A CN105017294 A CN 105017294A
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bct
coordination compound
dicarboxylic acid
preparation
thiadiazolyl group
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CN105017294B (en
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张巨文
李晓力
刘滨秋
蔡克迪
刘国成
阚晓敏
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Bohai University
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    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13Crystalline forms, e.g. polymorphs
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    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1018Heterocyclic compounds
    • C09K2211/1025Heterocyclic compounds characterised by ligands
    • C09K2211/1044Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1051Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
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    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
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  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

The present invention discloses a thiadiazole dicarboxylic acid terbium coordination compound, a preparation method and applications thereof, wherein the chemical formula of the coordination compound is Tb2(bct)3(H2O)5, bct is 2,5-bis(carboxymethylmercapto)-1,3,4-thiadiazole anion, the coordination compound contains two kinds of crystallographic independent Tb ions, the carboxy of the bct anion is connected with the Tb ions to form a binuclear Tb cluster and a one-dimensional Tb chain, the binuclear Tb cluster and the one-dimensional Tb chain are connected to form a two-dimensional layer, and the two-dimensional layer and the bct anion are connected to form a three-dimensional skeleton structure. The coordination compound of the present invention has the three-dimensional skeleton structure, exhibits the bifunctional characteristic of photoluminescence and ferromagnetic order, and can be possibly adopted as the magneto-optical dual functional material.

Description

A kind of thiadiazolyl group dicarboxylic acid terbium coordination compound and its preparation method and application
Technical field
The present invention relates to optomagnetic bifunctional material preparation field, be specifically related to a kind of thiadiazolyl group dicarboxylic acid terbium coordination compound and its preparation method and application.
Background technology
Various structure and make organolanthanide complexes be subject to the extensive concern of coordination chemistry worker in the potential application in the fields such as luminescence, magnetics.As everyone knows, owing to having strong coordination and charge balance ability, organic carboxylic acid compounds is widely used in preparing organolanthanide complexes.In recent years, as the organic carboxylic acid compounds that a class is important, synthesizing rare-earth a metal-organic complex is used to more and more containing nitronic acid.This is because this compounds not only possibility sensitization rare earth luminescence, and the magnetic property that the organolanthanide complexes to be constructed by this compounds also may have simultaneously, therefore use this compounds to prepare and have difunctional complex material that is luminous and magnetic property concurrently.2,5-two (carboxymethyl sulfydryl)-1,3,4-thiadiazoles acid is a kind of multiple tooth nitrogenous dicarboxylic acid of flexibility, based on its organolanthanide complexes also rare report.Therefore, being necessary synthesis and such organolanthanide complexes of structural characterization, studying its physicochemical property, to obtaining optomagnetic bifunctional material.
Summary of the invention
For solving the problem, the invention provides that a kind of synthetic method is simple, synthesis material cost is low, the thiadiazolyl group dicarboxylic acid terbium coordination compound showing good optomagnetic difunctional character and its preparation method and application.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of thiadiazolyl group dicarboxylic acid terbium coordination compound, it is characterized in that, the chemical formula of described title complex is Tb 2(bct) 3(H 2o) 5, in formula, bct is 2,5-two (carboxymethyl sulfydryl)-1,3,4-thiadiazoles negatively charged ion; Described title complex comprises two kinds of inspection crystalline substances independently Tb ion, and the carboxyl of bct negatively charged ion connects Tb ion and forms double-core Tb bunch and one dimension Tb chain, and double-core Tb bunch is connected to form two-dimensional layer with one dimension Tb chain, and two-dimensional layer and bct negatively charged ion are connected to form three dimensional skeletal structure.
For solving the problem, present invention also offers a kind of preparation method of thiadiazolyl group dicarboxylic acid terbium coordination compound, comprising the following steps:
S1, by terbium trichloride and 2,5-two (carboxymethyl sulfydryl)-1,3,4-thiadiazoles acid by after the mixed in molar ratio of 1: 2.5, add in deionized water, by NaOH solution adjust ph to 7;
S2, the solution of step S1 gained proceeded in autoclave be warming up to 120 degrees Celsius, be incubated 20 hours, be slowly down to room temperature and obtain white chunks crystal, filter and use deionized water wash, naturally drying, obtaining title complex.
Wherein, described terbium trichloride is TbCl 36H 2o, the add-on of deionized water is 30% of autoclave volume.
Wherein, the concentration of NaOH is 0.1mol/L.
Above-mentioned a kind of thiadiazolyl group dicarboxylic acid terbium coordination compound can be used as the application of optomagnetic bifunctional material.
The present invention has following beneficial effect:
1. synthetic method is simple, and synthesis material is easy to get, and cost is low, and output is high;
2. the thiadiazolyl group dicarboxylic acid terbium coordination compound poorly water-soluble synthesized under hydrothermal condition, common are also very difficult in machine solvent dissolving, prevents the secondary pollution to environment;
3. 2,5-two (carboxymethyl sulfydryls)-1,3, easily and terbium ion coordination, the introducing of its carboxyl anion is not only conducive to balancing charge to 4-thiadiazoles negatively charged ion, and adds the wetting ability of part, accelerate the crystallisation process of title complex, shorten synthesis cycle, reduce current consumption;
4. 2,5-two (carboxymethyl sulfydryl)-1,3,4-the flexibility of thiadiazoles negatively charged ion make it have coordination diversity, improve the productive rate of title complex, reduce cost;
5. thiadiazolyl group dicarboxylic acid terbium coordination compound presents the difunctional character of photoluminescence and ferromagnetic ordering, may apply as optomagnetic bifunctional material.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5the coordination environment figure of middle Tb ion;
Fig. 2 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5the structure iron of middle double-core Tb bunch (left side) and one dimension Tb chain (right side);
Fig. 3 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5two-dimensional layer structure iron;
Fig. 4 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5three dimensional skeletal structure figure;
Fig. 5 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5x-ray powder diffraction figure;
Fig. 6 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5thermogravimetric and differential thermal curve figure;
Fig. 7 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5room temperature solid excitation and emission spectra figure;
Fig. 8 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5luminescent lifetime figure (solid line is best-fit);
Fig. 9 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5the temperature-independent figure of DC magnetic susceptibility;
Figure 10 is embodiment of the present invention Tb 2(bct) 3(H 2o) 5field cold (FC) and null field cold (ZFC) magnetzation curve figure (illustration is partial enlargement).
Embodiment
In order to make objects and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment
By the TbCl of 0.1mmol 36H 22 of O and 0.25mmol, two (the carboxymethyl sulfydryl)-1 of 5-, 3, the acid of 4-thiadiazoles joins in 7mL deionized water successively, regulate the pH value to 7 of mixture with the NaOH solution 5mL of 0.1mol/L, then mixture is transferred in autoclave, be warming up to 120 degrees Celsius, be incubated 20 hours, be slowly down to room temperature and obtain white chunks crystal Tb 2(bct) 3(H 2o) 5, filter and use deionized water wash, naturally drying, obtaining title complex.
The sizeable monocrystalline of picking under the microscope, Bruker SMART APEX II type X-ray single crystal diffractometer is used at room temperature to collect diffraction data, SADABS program is used to carry out absorption correction to diffraction data, use SAINT and SHELXTL program to resolve diffraction data, use method of least squares to carry out refine to crystalline structure.Fig. 1 to Fig. 4 is Tb 2(bct) 3(H 2o) 5crystalline structure figure, wherein Fig. 1 is Tb 2(bct) 3(H 2o) 5coordination environment figure, display Tb 2(bct) 3(H 2o) 5comprise two kinds of inspection crystalline substances independently Tb ion (Tb1 and Tb2); Fig. 2 is that the carboxyl of bct negatively charged ion connects double-core Tb bunch of the formation of Tb ion and the structure iron of one dimension Tb chain; Fig. 3 is the two-dimensional layer structure iron that bct negatively charged ion connects above-mentioned double-core Tb bunch and one dimension Tb chain formation; Fig. 4 is the three dimensional skeletal structure figure that bct negatively charged ion connects above-mentioned two-dimensional layer formation.
Rigaku Ultima IV type x-ray powder diffraction instrument is used to collect powder diffraction data, scan pattern is 2 θ/θ, sweep limit is 5 to 50 degree, uses Cerius2 program matching powder diffraction data, uses Mercury1.4.1 software to carry out the powdery diffractometry simulation of single crystal structure.Fig. 5 is Tb 2(bct) 3(H 2o) 5powder diagram, the powder diagram of actual measurement and the basically identical of simulation, indicate the phase purity of bulk article.
Use PE-Pyris Diamond S-II type thermal analyzer to collect thermogravimetric and differential thermal data, heating rate is 10 DEG C/min, and temperature range is 30 to 800 degrees Celsius.Fig. 6 is Tb 2(bct) 3(H 2o) 5thermogravimetric and differential thermal curve figure, Tb 2(bct) 3(H 2o) 5in 160 to 200 degree celsius temperature intervals, lose coordinated water molecule, then kept stable, until 280 degrees Celsius of skeletons start to cave in, show that bulk article has certain thermostability.
FLS 920 type steady-state fluorescence and phosphorescent lifetime spectrograph is used to collect photoluminescence data.Fig. 7 is Tb 2(bct) 3(H 2o) 5room temperature solid excitation and emission spectra figure, show the Tb ionoluminescence of the green of strong bct part sensitization; Fig. 8 is Tb 2(bct) 3(H 2o) 5luminescent lifetime figure, show Tb 2(bct) 3(H 2o) 5there is relatively long luminescent lifetime.
Quantum Design MPMSXL7 type Superconducting magnetic determinator is used to collect DC magnetic data.Fig. 9 is Tb 2(bct) 3(H 2o) 5the temperature-independent figure of DC magnetic susceptibility, display Tb 2(bct) 3(H 2o) 5there is obvious ferromagnetic interaction in middle Tb interionic, and may there is ferromagnetic ordering phenomenon; Figure 10 is Tb 2(bct) 3(H 2o) 5field cold (FC) and null field cold (ZFC) magnetzation curve figure, demonstrate Tb further 2(bct) 3(H 2o) 5ferromagnetic ordering behavior.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (5)

1. a thiadiazolyl group dicarboxylic acid terbium coordination compound, is characterized in that, the chemical formula of described title complex is Tb 2(bct) 3(H 2o) 5, in formula, bct is 2,5-two (carboxymethyl sulfydryl)-1,3,4-thiadiazoles negatively charged ion; Described title complex comprises two kinds of inspection crystalline substances independently Tb ion, and the carboxyl of bct negatively charged ion connects Tb ion and forms double-core Tb bunch and one dimension Tb chain, and double-core Tb bunch is connected to form two-dimensional layer with one dimension Tb chain, and two-dimensional layer and bct negatively charged ion are connected to form three dimensional skeletal structure.
2. a preparation method for thiadiazolyl group dicarboxylic acid terbium coordination compound, is characterized in that, comprises the following steps:
S1, by terbium trichloride and 2,5-two (carboxymethyl sulfydryl)-1,3,4-thiadiazoles acid by after the mixed in molar ratio of 1: 2.5, add in deionized water, by NaOH solution adjust ph to 7;
S2, the solution of step S1 gained proceeded in autoclave be warming up to 120 degrees Celsius, be incubated 20 hours, be slowly down to room temperature and obtain white chunks crystal, filter and use deionized water wash, naturally drying, obtaining title complex.
3. the preparation method of thiadiazolyl group dicarboxylic acid terbium coordination compound according to claim 2, it is characterized in that, the add-on of deionized water is 30% of autoclave volume.
4. the preparation method of thiadiazolyl group dicarboxylic acid terbium coordination compound according to claim 2, it is characterized in that, the concentration of NaOH is 0.1mol/L.
5. the application of a kind of thiadiazolyl group dicarboxylic acid terbium coordination compound as claimed in claim 1, is characterized in that, use as optomagnetic bifunctional material.
CN201510335431.8A 2015-06-12 2015-06-12 A kind of thiadiazolyl group dicarboxylic acids terbium coordination compound and its preparation method and application Expired - Fee Related CN105017294B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096498A (en) * 2018-08-27 2018-12-28 广东工业大学 A kind of New Two Dimensional conductive metal organic framework material and preparation method thereof
CN114716688A (en) * 2022-05-17 2022-07-08 山西大学 Terbium complex and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WANG Y T.ET AL: ""Synthesis, Crystal Structure and Characterizations of a Novel 3D Coordinated Polymer [Gd2(tzda)3(H2O)5]n [H2tzda=(1,3,4-Thiadiazole-2,5-diyldithio)diacetic Acid]"", 《SYNTHESIS AND REACTIVITY IN INORGANIC, METAL-ORGANIC AND NANO-METAL CHEMISTRY》 *
王宇婷等: ""三维配位聚合物[Ce4(tzda)6(H2O)10]n的水热合成和晶体结构"", 《郑州大学学报(理学版)》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096498A (en) * 2018-08-27 2018-12-28 广东工业大学 A kind of New Two Dimensional conductive metal organic framework material and preparation method thereof
CN114716688A (en) * 2022-05-17 2022-07-08 山西大学 Terbium complex and preparation method and application thereof
CN114716688B (en) * 2022-05-17 2022-12-30 山西大学 Terbium complex and preparation method and application thereof

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