CN104211660A - Lanthanum complex as well as preparation method and application thereof - Google Patents

Lanthanum complex as well as preparation method and application thereof Download PDF

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Publication number
CN104211660A
CN104211660A CN201410448181.4A CN201410448181A CN104211660A CN 104211660 A CN104211660 A CN 104211660A CN 201410448181 A CN201410448181 A CN 201410448181A CN 104211660 A CN104211660 A CN 104211660A
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coordination
lanthanide complex
tdzdc
ion
preparation
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赵振新
马步伟
王永胜
王立夫
张军帅
吕春旺
董英英
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Henan University of Urban Construction
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Henan University of Urban Construction
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D285/00Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01Five-membered rings
    • C07D285/02Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/101,2,5-Thiadiazoles; Hydrogenated 1,2,5-thiadiazoles
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

The invention discloses a lanthanum complex, a preparation method of the lanthanum complex, and an application of the lanthanum complex. The chemical composition of the lanthanum complex is C12La2N6O17S3H10. The compound is prepared by adopting a solvothermal method, an obtained crystal is relatively high in yield and purity, and crystal analysis shows that the space group of the compound is P21 and is a two-nuclear lanthanum cluster structure formed by H2tdzdc and two La<3+> ions; each La1<3+> ion is coordinated with four H2tdzdc ligands in an N,O- and O,O'- chelating coordination mode, and one terminal water molecule also participates in coordination; each La2<3+> ion forms coordination with five H2tdzdc ligands by virtue of N,O-different-tooth chelating coordination and O,O'- chelating coordination modes. The coordination binding site of each H2tdzdc ligand is occupied by three La<3+> ions so as to form a three-dimensional network connection structure. A coordination polymer disclosed by the invention can be used as potential energy converters and solid luminescent materials, and has good application prospects in the field of material science.

Description

A kind of Lanthanide complex and preparation method thereof and application
Technical field
The present invention relates to multi-nuclear metal cluster compound, be specially a kind of Lanthanide complex and preparation method thereof and application.
Background technology
In recent years, the multi-nuclear metal cluster compound synthesized by the coordination of metal ion and organic ligand has caused the great interest of people.They not only have novel structure, and show interesting character or function (Sessoli, R.; Tsai, H.-L.; Schake, A. R.; Wang, S.; Vincent, J. B.; Folting, K.; Gatteschi, D.; Christou, G.; Hendrickson, D. N. J. Am. Chem. Soc. 1993,115,1804; Delfs, C.; Gatteschi, D.; Pardi, L.; Sessoli, R.; Wieghardt, K.; Hande, D. Inorg. Chem. 1993,32,3099.).Because this compounds has specific restriction for the selection of source metal and part, thus design and construct this kind of crystalline material with special construction and performance and there is very large challenge.A kind of strategy is had to be that source metal adopts the method for conventional volatilization to synthesize with metal precursor.From synthetic method aspect, solvent-thermal process is a kind of method of effective this compounds of synthesis.(Zeng,?Y.?F.;?Hu,?X.;?Xue,?L.;?Liu,?S.?J.;?Hu,?T.?L.;?Bu,?X.?H.?Inorg.?Chem.?2012,?51,?9571;?Han,?S.?D.;?Song,?W.?C.;?Zhao,?J.?P.;?Yang,?Q.;?Liu,?S.?J.;?Li,?Y.;?Bu?X.?H.?Chem.?Commun.,?2013,?49,?871.)。The synthesis of this kind of material and exploration, first provide reliable experimental basis to metal cluster synthesis, carry out systematic study in addition significant to the magnetic of such material.
 
Summary of the invention
The object of the present invention is to provide a kind of Lanthanide complex and preparation method thereof, this title complex is a kind of title complex with two core lanthanums bunch " lanthanum-1; 2; 5-thiadiazoles-3; 4-diacid-water ", photoluminescent property shows under the optical excitation of 260nm, and title complex can at 386nm, 426nm(purple) and 461nm(blue) go out to send fluorescence.
The object of the present invention is achieved like this:
A kind of Lanthanide complex, its chemical formula is: C 12la 2n 6o 17s 3h 10(1); Wherein main part is 1,2,5-thiadiazoles-3,4-diacid (H 2tdzdc), solvent is: second alcohol and water; Main infrared absorption peak is 3427 cm – 1, 1625 cm – 1, 1516 cm – 1, 1306 cm – 1, 1058 cm – 1, 1014 cm – 1, 800 cm – 1with 744 cm – 1; Co-ordinating backbone decomposition temperature is 400 DEG C.
The crystal of described Lanthanide complex belongs to triclinic(crystalline)system, and spacer is p2 1, unit cell parameters is respectively: a=6.9884 (14), b=12.991 (3), c=13.554 (3), α= γ=90 o, β=100.29 o;
The crystal of described Lanthanide complex is a kind of by H 2tdzdc part and two kinds of La 3+the two core lanthanum clustering architectures that ion is formed; Each La1 3+ion with N, O-and O, O '-chelating coordination modes and 4 H 2tdzdc ligands, has end-point water to participate in coordination simultaneously; Each La2 3+ion is by the different tooth chelating ligands of N, O-and O, O '-chelating coordination modes and 5 H 2tdzdc part forms coordination.And for each H 2tdzdc part, its coordination binding site is by 3 La 3+ion occupies, thus forms a three-dimensional network syndeton;
The preparation method of described Lanthanide complex is: by 1,2,5-thiadiazoles-3,4-diacid, La (NO 3) 36H 2o, 5% NaOH solution join in the mixed solvent of distilled water and ethanol, gained mixture is obtained colourless transparent crystal by solvent thermal reaction, then uses water, alcohol flushing respectively successively, and in air drying;
1,2,5-described thiadiazoles-3,4-diacid and La (NO 3) 36H 2o mol ratio is 1:1 ~ 2:1;
Described distilled water and the solvent ratio of ethanol are 3:2 ~ 2:1;
The solvent thermal condition of described thermal response, for react 2-4 days at 140 ~ 160 DEG C, naturally cools to room temperature;
Being applied as of described Lanthanide complex: fluorometric investigation shows under the optical excitation of 260nm, title complex can go out send purple fluorescence at 386nm and 426nm, goes out to send blue-fluorescence at 461nm, can be used as energy transfer machine and solid luminescent material.
positive beneficial effect:the invention discloses a kind of Lanthanide complex and its preparation method and application, its chemical constitution is: C 12la 2n 6o 17s 3h 10; This compound adopts solvent-thermal method preparation, and the crystal yield of gained and purity are all higher, and crystal is resolved and shown that its spacer is p21, be a kind of by H 2tdzdc part and two kinds of La 3+the two core lanthanum clustering architectures that ion is formed; Each La1 3+ion with N, O-and O, O '-chelating coordination modes and 4 H 2tdzdc ligands, has end-point water to participate in coordination simultaneously; Each La2 3+ion is by the different tooth chelating ligands of N, O-and O, O '-chelating coordination modes and 5 H 2tdzdc part forms coordination.And for each H 2tdzdc part, its coordination binding site is by 3 La 3+ion occupies, thus forms a three-dimensional network syndeton.Fluorometric investigation shows with under the optical excitation of 260nm, and title complex can at 386nm, 426nm(purple) and 461nm(blue) go out to send fluorescence.Therefore, this ligand polymer can be used as potential energy transfer machine and solid luminescent material, has a good application prospect at material science.
 
Accompanying drawing explanation
Fig. 1 is that coordination mode of the present invention and polyhedron are shown;
Fig. 2 is that IR of the present invention schemes;
Fig. 3 is that TG of the present invention schemes;
Fig. 4 is fluorescence spectrum figure of the present invention;
In Fig. 1: the coordination mode that (a) is La1; B coordination mode that () is La2; C () is H 2the coordination mode of tdzdc; D () is along the axial one-dimensional channels of a.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described further:
A kind of Lanthanide complex, its chemical formula is: C 12la 2n 6o 17s 3h 10(1); Wherein main part is 1,2,5-thiadiazoles-3,4-diacid (H 2tdzdc), solvent is: second alcohol and water; Main infrared absorption peak is 3427 cm – 1, 1625 cm – 1, 1516 cm – 1, 1306 cm – 1, 1058 cm – 1, 1014 cm – 1, 800 cm – 1with 744 cm – 1; Co-ordinating backbone decomposition temperature is 400 DEG C.
The crystal of described Lanthanide complex belongs to triclinic(crystalline)system, and spacer is p21, unit cell parameters is respectively: a=6.9884 (14), b=12.991 (3), c=13.554 (3), α= γ=90 o, β=100.29 o;
The crystal of described Lanthanide complex is a kind of by H 2tdzdc part and two kinds of La 3+the two core lanthanum clustering architectures that ion is formed; Each La1 3+ion with N, O-and O, O '-chelating coordination modes and 4 H 2tdzdc ligands, has end-point water to participate in coordination simultaneously; Each La2 3+ion is by the different tooth chelating ligands of N, O-and O, O '-chelating coordination modes and 5 H 2tdzdc part forms coordination.And for each H 2tdzdc part, its coordination binding site is by 3 La 3+ion occupies, thus forms a three-dimensional network syndeton;
The preparation method of described Lanthanide complex is: by 1,2,5-thiadiazoles-3,4-diacid, La (NO 3) 36H 2o, 5% NaOH solution join in the mixed solvent of distilled water and ethanol, gained mixture is obtained colourless transparent crystal by solvent thermal reaction, then uses water, alcohol flushing respectively successively, and in air drying;
1,2,5-described thiadiazoles-3,4-diacid and La (NO 3) 36H 2o mol ratio is 1:1 ~ 2:1;
Described distilled water and the solvent ratio of ethanol are 3:2 ~ 2:1;
The solvent thermal condition of described thermal response, for react 2-4 days at 140 ~ 160 DEG C, naturally cools to room temperature;
Being applied as of described Lanthanide complex: fluorometric investigation shows under the optical excitation of 260nm, title complex can go out send purple fluorescence at 386nm and 426nm, goes out to send blue-fluorescence at 461nm, can be used as energy transfer machine and solid luminescent material.
embodiment 1
The preparation of Lanthanide complex:
Take 1,2,5-thiadiazoles-3,4-diacid (105 milligrams), La (NO 3) 36H 2o(260 milligram) be placed in 20 milliliters of autoclaves, add 6 ml distilled waters and 4 milliliters of ethanol, stirring at room temperature sealed after 10 minutes; React 2 days at 160 DEG C, obtain colourless transparent crystal, then use water, washing with alcohol respectively successively, and in air drying;
Sign to embodiment 1 Lanthanide complex:
(1) infrared spectra, thermogravimetric measure:
As shown in Figure 2 and Figure 3, ir data is collected on TENSOR 27 OPUS (BRUKER) Fourier transformation infrared spectrometer and completes, KBr compressing tablet, recording interval 4000 ~ 400cm -1.Thermogravimetric analysis PERKIN-ELMER-7 type differential thermal thermogravimetric analyzer completes, air atmosphere, temperature elevating range 15 ~ 700 DEG C, heat-up rate 10 DEG C/min.
(2) crystal structure determination
Choose the monocrystalline of suitable size under the microscope, under low temperature, T=293K is on Rigaku RAXIS-RAPID diffractometer, with the Mo-K through graphite monochromator monochromatization aray ( l=0.71073), with w-φmode collects diffraction data; All diffraction datas use SADABS program to carry out absorption correction.Unit cell parameters method of least squares is determined; Reduction of data and structure elucidation use SAINT and SHELXTL program to complete respectively; First determine whole non-hydrogen atom coordinate by difference functions method and method of least squares, and obtain the hydrogen atom position of main body framework with theoretical hydrogenation method, then by method of least squares, refine is carried out to crystalline structure.Structure is shown in Fig. 1.The partial parameters of the data gathering of crystallography point diffraction and structure refinement is listed in shown in following table.
(3) the photoluminescent property research of Lanthanide complex: as shown in Figure 4, fluorometric investigation uses F-4500 fluorescence spectrophotometer to complete.
A kind of Lanthanide complex disclosed by the invention and its preparation method and application, its chemical constitution is: C 12la 2n 6o 17s 3h 10; This compound adopts solvent-thermal method preparation, and the crystal yield of gained and purity are all higher, and crystal is resolved and shown that its spacer is p21, be a kind of by H 2tdzdc part and two kinds of La 3+the two core lanthanum clustering architectures that ion is formed; Each La1 3+ion with N, O-and O, O '-chelating coordination modes and 4 H 2tdzdc ligands, has end-point water to participate in coordination simultaneously; Each La2 3+ion is by the different tooth chelating ligands of N, O-and O, O '-chelating coordination modes and 5 H 2tdzdc part forms coordination.For each H 2tdzdc part, its coordination binding site is by 3 La 3+ion occupies, thus forms a three-dimensional network syndeton.Fluorometric investigation shows with under the optical excitation of 260nm, and title complex can at 386nm, 426nm(purple) and 461nm(blue) go out to send fluorescence.Therefore, this ligand polymer can be used as potential energy transfer machine and solid luminescent material, has a good application prospect at material science.
Above case study on implementation is only for illustration of the preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; in the ken that described exercising ordinary skill possesses; the any amendment done within the spirit and principles in the present invention, equivalent to substitute and improvement etc., the protection domain of the application all should be considered as.

Claims (8)

1. a Lanthanide complex, is characterized in that: its chemical formula is: C 12la 2n 6o 17s 3h 10(1); Wherein main part is 1,2,5-thiadiazoles-3,4-diacid (H 2tdzdc), solvent is: second alcohol and water; Main infrared absorption peak is 3427 cm – 1, 1625 cm – 1, 1516 cm – 1, 1306 cm – 1, 1058 cm – 1, 1014 cm – 1, 800 cm – 1with 744 cm – 1; Co-ordinating backbone decomposition temperature is 400 DEG C.
2. the crystal of Lanthanide complex as claimed in claim 1, it is characterized in that: belong to triclinic(crystalline)system, spacer is p2 1, unit cell parameters is respectively: a=6.9884 (14), b=12.991 (3), c=13.554 (3), α= γ=90 o, β=100.29 o.
3. the crystal of Lanthanide complex according to claim 2, is characterized in that: the crystal of described Lanthanide complex is a kind of by H 2tdzdc part and two kinds of La 3+the two core lanthanum clustering architectures that ion is formed; Each La1 3+ion with N, O-and O, O '-chelating coordination modes and 4 H 2tdzdc ligands, has end-point water to participate in coordination simultaneously; Each La2 3+ion is by the different tooth chelating ligands of N, O-and O, O '-chelating coordination modes and 5 H 2tdzdc part forms coordination; And for each H 2tdzdc part, its coordination binding site is by 3 La 3+ion occupies, thus forms a three-dimensional network syndeton.
4. Lanthanide complex as claimed in claim 1, its preparation method is: by 1,2,5-thiadiazoles-3,4-diacid, La (NO 3) 36H 2o, 5% NaOH solution join in the mixed solvent of distilled water and ethanol, gained mixture is obtained colourless transparent crystal by solvent thermal reaction, then uses water, alcohol flushing respectively successively, and in air drying.
5. the preparation method of Lanthanide complex according to claim 4, is characterized in that: 1,2,5-described thiadiazoles-3,4-diacid and La (NO 3) 36H 2o mol ratio is 1:1 ~ 2:1.
6. the preparation method of Lanthanide complex according to claim 4, is characterized in that: described distilled water and the solvent ratio of ethanol are 3:2 ~ 2:1.
7. the preparation method of Lanthanide complex according to claim 4, is characterized in that: the solvent thermal condition of described thermal response, for react 2-4 days at 140 ~ 160 DEG C, naturally cools to room temperature.
8. Lanthanide complex as claimed in claim 1, it is applied as: fluorometric investigation shows under the optical excitation of 260nm, title complex can go out send purple fluorescence at 386nm and 426nm, goes out to send blue-fluorescence at 461nm, can be used as energy transfer machine and solid luminescent material.
CN201410448181.4A 2014-09-04 2014-09-04 Lanthanum complex as well as preparation method and application thereof Pending CN104211660A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107603599A (en) * 2017-10-01 2018-01-19 桂林理工大学 A kind of Lanthanide complex blue emitting material and synthetic method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102633823A (en) * 2012-02-23 2012-08-15 沈阳化工大学 Rare-earth metal complex and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN102633823A (en) * 2012-02-23 2012-08-15 沈阳化工大学 Rare-earth metal complex and preparation method thereof

Non-Patent Citations (1)

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Title
赵婷婷: "基于唑类二羧酸配体的配位聚合物的合成", 《中国博士学位论文全文数据库 工程科技I辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107603599A (en) * 2017-10-01 2018-01-19 桂林理工大学 A kind of Lanthanide complex blue emitting material and synthetic method

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