CN104211660A - Lanthanum complex as well as preparation method and application thereof - Google Patents
Lanthanum complex as well as preparation method and application thereof Download PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- coordination
- lanthanide complex
- tdzdc
- ion
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/10—1,2,5-Thiadiazoles; Hydrogenated 1,2,5-thiadiazoles
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
Landscapes
- 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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410448181.4A CN104211660A (en) | 2014-09-04 | 2014-09-04 | Lanthanum complex as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410448181.4A CN104211660A (en) | 2014-09-04 | 2014-09-04 | Lanthanum complex as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104211660A true CN104211660A (en) | 2014-12-17 |
Family
ID=52093611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410448181.4A Pending CN104211660A (en) | 2014-09-04 | 2014-09-04 | Lanthanum complex as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104211660A (en) |
Cited By (1)
| 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)
| 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 |
-
2014
- 2014-09-04 CN CN201410448181.4A patent/CN104211660A/en active Pending
Patent Citations (1)
| 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)
| 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)
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Meyer et al. | The dynamic chemistry of molecular Borromean rings and Solomon knots | |
| CN103588799B (en) | A kind of cadmium coordination polymer and its preparation method and application | |
| Hu et al. | Iodine-templated assembly of unprecedented 3d–4f metal–organic frameworks as photocatalysts for hydrogen generation | |
| Yin et al. | Role of molar-ratio, temperature and solvent on the Zn/Cd 1, 2, 4-triazolate system with novel topological architectures | |
| CN101787043B (en) | Novel light-emitting transition metal organic framework structured compound and preparation method thereof | |
| Wu et al. | Two unprecedented 3D metal–organic polyrotaxane frameworks based on a new flexible tri (imidazole) ligand | |
| CN106866988A (en) | A kind of layer column type metal-organic framework material as well as preparation method and application thereof | |
| CN101531671B (en) | Micro-porous copper coordination polymer, preparation method and application thereof | |
| Wei et al. | A series of inorganic–organic hybrid cadmium borates with novel Cd-centred [Cd@ B 14 O 20 (OH) 6] 2− clusters | |
| Castagnetto et al. | Absolute configurational assignment of self‐organizing asymmetric tripodal ligand‐metal complexes | |
| CN104628751A (en) | Luminous porous coordination polymer as well as preparation method and application thereof | |
| Katsenis et al. | High-spin Ni (II) clusters: triangles and planar tetranuclear complexes | |
| CN104211660A (en) | Lanthanum complex as well as preparation method and application thereof | |
| Zhang et al. | Based on a V-shaped In (III) metal–organic framework (MOF): Design, synthesis and characterization of diverse physical and chemical properties | |
| Dong et al. | Different crystal structures and luminescent properties of zinc and cadmium coordination polymers constructed from two flexible thioether ligands with different alkyl chains | |
| Zhao et al. | A study of zinc (II) coordination polymers with identical meso-helix based on 1, 4-bis (2-methyl-imidazol-1-yl) butane | |
| CN102532175A (en) | Rare earth coordination polymer taking 2, 2'-bipyridyl as template as well as preparation method and application thereof | |
| Tang et al. | Synthesis, structure and XPS of a novel two-dimensional CuII–EuIII heterometallic–organic framework | |
| Zhou et al. | Synthesis, structures and photoluminescence of three d10 5-aminonicotinate and 5-aminoisophthalate coordination polymers with bilayer structures | |
| CN104130292A (en) | Three dimensional coordination polymer with double core structure and preparation method thereof | |
| Ge et al. | Luminescent cluster-organic frameworks constructed from predesigned supertetrahedral {Ln4Zn6} secondary building units | |
| CN107200850A (en) | It is a kind of that there is the Porous coordination polymer of identification function to aromatic molecules, prepare and apply | |
| CN104130293B (en) | A kind of three-dimensional coordination polymer of mixed ligand and preparation method thereof | |
| Li et al. | A {CoII9CoIII3} dodecanuclear cluster based on o-vanillin oxime: Synthesis, structures and properties | |
| Çiftçi et al. | Cobalt (II), Zinc (II) and Cadmium (II) Coordination Polymers Assembled by Flexible 5, 5′-(But-2-ene-1, 4-diylbis (oxy)) diisophthalic Acid and 1, 2-Bis ((1 H-imidazol-1-yl) methyl) benzene Ligands |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141217 |
|
| WD01 | Invention patent application deemed withdrawn after publication |