CN102286008A - Xanthene-9-cadmium carboxylate complex and preparation method thereof - Google Patents
Xanthene-9-cadmium carboxylate complex and preparation method thereof Download PDFInfo
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- CN102286008A CN102286008A CN2010102782236A CN201010278223A CN102286008A CN 102286008 A CN102286008 A CN 102286008A CN 2010102782236 A CN2010102782236 A CN 2010102782236A CN 201010278223 A CN201010278223 A CN 201010278223A CN 102286008 A CN102286008 A CN 102286008A
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- carboxylic acid
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Abstract
The invention discloses a xanthene-9-cadmium carboxylate complex and a preparation method thereof, belonging to the field of d10 metal complex fluorescent materials. The complex has a chemical formula as follows: [Cd(L)2(CH3OH)2] infinity, wherein L=xanthene-9-carboxy-anionic coordinate. The complex is synthesized by using a solvent volatilizing method which comprises the following steps: dissolving the complex xanthene-9-carboxylic acid (HL) by using methyl alcohol, adding a certain quantity of 2,6-dimethyl pyridine, and stirring uniformly; then adding metal cadmium salt, filtering after stirring and dissolving, and then standing for volatilizing for 5-8 days to obtain a colorless massive monocrystal. The synthesis process has the advantages of simplicity, convenience in operation, good stability, high productivity, good reproducibility and the like. The obtained solid material is expected to be further researched and developed in the field of fluorescent materials.
Description
Technical field
The invention belongs to d
10Metal complex fluorescent material field, especially a kind of xanthene-9-carboxylic acid cadmium complex and preparation method thereof.
Background technology
The synthetic d of design with novel structure and specific function
10Metal complexes receives people's very big concern in recent years always.Much shown potential superior application performance in them, as (S.Leininger, B.Olenyuk, P.J.Stang, Chem.Rev.2000,100,853-908 such as optics, catalysis, fractionation by adsorption and biological activitys; S.Wang, Coord.Chem.Rev.2001,215,79-98; O.R.Evans, W.Lin, Acc.Chem.Res.2002,35,511-522; P.J.Steel, Acc.Chem.Res.2005,38,243-250; B.-H.Ye, M.-L.Tong, X.-M.Chen, Coord.Chem.Rev.2005,249,545-565).The carboxylic-acid part receives people's very big concern always in ligand polymer is constructed, such ligand moiety or all take off proton makes part show various coordination mode flexibly, obtains the compound of different structure.About the existing a large amount of report of the ligand polymer of carboxylic-acid part, particularly fragrance contains carboxylic-acid parts such as phenyl ring, naphthalene nucleus, anthracene nucleus and derivative series thereof by the extensive and a large amount of research of people.
For oxa anthracenes carboxylic acid part, compare with the carboxylic acid part that contains phenyl ring, naphthalene nucleus, anthracene nucleus and to have following tangible characteristics: (1) has the conjugated pi system, therefore π when constructing the corresponding metal title complex ... pi accumulation and C-H ... π interacts may play important effect, particularly enters the more supramolecule network facet of higher-dimension at limited multinuclear subunit and the low-dimensional molecular entity of connection; (2) the volume obstacle of oxa-anthracene nucleus exerts an influence to the coordination mode and the ability of carboxyl, but also is in the network from the angle of crystal engineering weak interaction and molecular geometry and internetwork π ... pi accumulation and C-H ... the condition that the interactional formation of π is provided convenience; (3) anthracene nucleus that contains the conjugated pi system is good fluorescent signal chromophoric group, thus contain this type of ligand-complexes synthetic also for fluorescent material and the exploitation (as: electroluminescent, chemical sensor, fluorescence PET transmitter) of further using thereof provide may.
Contain carboxylic-acid parts such as phenyl ring, naphthalene nucleus, anthracene nucleus and derivative series thereof with the above-mentioned fragrance of mentioning and compare, contain the carboxylic acid part of xanthene ring system row, xanthene-9-carboxylic acid for example, the unmanned so far report of the research of its metal complexes.
Summary of the invention
The object of the present invention is to provide a kind of xanthene-9-carboxylic acid cadmium complex and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is as follows:
The cadmium complex of xanthene of the present invention-9-carboxylic acid, title complex are the title complexs of following chemical formula: [Cd (L)
2(CH
3OH)
2]
∞, L=xanthene-9-carboxyl anion part wherein, the structural formula of L is as follows:
Described complex crystal belongs to oblique system, and spacer is P2 (1)/c, and unit cell parameters is
α=90 °, β=105.859 (12) °, γ=90 °,
Basic structure is a chain, has a kind of Cd
IISeven coordination environments.
The synthetic solvent flashing method of this title complex that is: under the room temperature, with part HL dissolve with methanol, adds 2 then, and the 6-lutidine stirs; Add the metal cadmium salt again, the stirring and dissolving after-filtration, gained filtrate is left standstill volatilization and was obtained colourless bulk-shaped monocrystal in 5-8 days, and successively with distilled water, ethanol and ether washing, drying obtains again.
Described part HL is dissolved in the solution of making in the methyl alcohol, and the concentration of part HL is 0.02～0.05molL
-1
The mol ratio of described part HL and metal cadmium salt is 1: 1～1: 2.
In the methanol solution of part HL, add 2, the mol ratio of 6-lutidine and part HL is 1: 1～3: 1.
The fluorescence data of crystal prototype of the present invention shows that this type of title complex has the stable fluorescence performance, can be used as fluorescent material and is applied at material science.The thermogravimetric analysis of title complex characterizes and shows that its skeleton still can stable existence about 140 ℃, for its further Application and Development as material provides the thermostability assurance.
The synthetic method of title complex provided by the invention adopts the solvent evaporation method synthetic compound.This synthetic method at normal temperatures and pressures, mild condition, productive rate height, reproducibility are good.
Description of drawings
Ca in this title complex of Fig. 1
IICoordination environment figure;
The one-dimensional chain structure iron of this title complex of Fig. 2;
The solid state fluorescence spectrogram of this title complex of Fig. 3;
The test of the powdery diffractometry of this title complex of Fig. 4 (XPRD) and theoretical contrast figure;
The thermogravimetric curve figure of this title complex of Fig. 5.
Embodiment
Complex crystal of the present invention is characterized in that described complex crystal belongs to oblique system, and spacer is P2 (1)/c, it is characterized in that described complex crystal belongs to oblique system, and spacer is that (10/c, unit cell parameters is P2
α=90 °, β=105.859 (12) °, γ=90 °,
Basic structure is a chain, has a kind of Cd
IICoordination environment, Cd
IISeven coordination configurations for distortion.
In the preparation method of title complex of the present invention, part HL is dissolved in and makes solution in the methyl alcohol, and concentration is 0.02～0.05molL
-1, the mol ratio of part HL and metal cadmium salt is 1: 1～1: 2; Methanol solution at part HL adds 0.03～0.05mL2,6-lutidine.
With 0.05mmol HL 2mL dissolve with methanol, it is excessive 2 to add, and the about 0.05mL of 6-lutidine stirs, and adds 0.05mmol Cd (ClO again
4)
26H
2O, the stirring and dissolving after-filtration leaves standstill volatilization then and obtained colourless bulk-shaped monocrystal in 5-8 days.Crystal washs with distilled water, ethanol and ether successively, vacuum-drying, and productive rate is about 55%.Main infrared absorption peak is: 3443m (br), 1604m, 1573s, 1482s, 1454m, 1381m, 1326w, 1304w, 1259vs, 1211w, 1183w, 1154w, 1120w, 1097w, 1036w, 941w, 871w, 801w, 746m, 664w, 570w, 490w.
With 0.1mmol HL 5mL dissolve with methanol, it is excessive 2 to add, and the about 0.05mL of 6-lutidine stirs, and adds 0.1mmol Cd (ClO again
4)
26H
2O, the stirring and dissolving after-filtration leaves standstill volatilization then and obtained colourless bulk-shaped monocrystal in 5-8 days.Crystal washs with distilled water, ethanol and ether successively, vacuum-drying, and productive rate is about 60%.Main infrared absorption peak is: 3443m (br), 1604m, 1573s, 1482s, 1454m, 1381m, 1326w, 1304w, 1259vs, 1211w, 1183w, 1154w, 1120w, 1097w, 1036w, 941w, 871w, 801w, 746m, 664w, 570w, 490w.
With 0.05mmol HL 2mL dissolve with methanol, it is excessive 2 to add, and the about 0.03mL of 6-lutidine stirs, and adds 0.05mmol Cd (NO again
3)
22H
2O, the stirring and dissolving after-filtration leaves standstill volatilization then and obtained colourless bulk-shaped monocrystal in 5-8 days.Crystal washs with distilled water, ethanol and ether successively, vacuum-drying, and productive rate is about 52%.Main infrared absorption peak is: 3443m (br), 1604m, 1573s, 1482s, 1454m, 1381m, 1326w, 1304w, 1259vs, 1211w, 1183w, 1154w, 1120w, 1097w, 1036w, 941w, 871w, 801w, 746m, 664w, 570w, 490w.
With 0.05mmol HL 2mL dissolve with methanol, it is excessive 2 to add, and the about 0.03mL of 6-lutidine stirs, and adds 0.05mmol CdCl again
2, the stirring and dissolving after-filtration leaves standstill volatilization then and obtained colourless bulk-shaped monocrystal in 5-8 days.Crystal washs with distilled water, ethanol and ether successively, vacuum-drying, and productive rate is about 58%.Main infrared absorption peak is: 3443m (br), 1604m, 1573s, 1482s, 1454m, 1381m, 1326w, 1304w, 1259vs, 1211w, 1183w, 1154w, 1120w, 1097w, 1036w, 941w, 871w, 801w, 746m, 664w, 570w, 490w.
The relevant characterization of title complex
(1) crystal structure determination of title complex
The monocrystalline of choosing suitable size at microscopically at room temperature carries out the X-ray diffraction experiment.At Xcalibur, Eos on the Gemini diffractometer, uses the Mo-K through the graphite monochromator monochromatization
αRay
With
Mode is collected diffraction data.Use CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.55 program is carried out reduction of data.The diffraction data of part-structure carries out absorption correction with the SADABS program.Crystalline structure is solved in conjunction with difference Fourier is synthetic by direct method.All non-hydrogen atom coordinate and anisotropic parameters carry out the complete matrix least-squares refinement, and the hydrogen atom position is determined by theoretical mode computation.Hydrogen atom on partial solvent water and the methyl alcohol is handled with the method for difference Fourier peak-seeking.Detailed axonometry data see Table 1; Important bond distance and bond angle data see Table 2.Crystalline structure is seen Fig. 1 and Fig. 2.
(2) the solid fluorescence performance study of title complex
Complex crystal sample after enrichment is handled is through further milled processed, and carry out the test of solid fluorescence: title complex excites at the 418nm place, obtains maximum emission peak at the 485nm place, sees Fig. 3.(instrument model: HITACHI/F-7000).
(3) the XPRD phase purity of title complex characterizes
The XPRD of title complex characterizes and shows that it has reliable phase purity, for its application as fluorescent material provides assurance, sees Fig. 4.(instrument model: Bruker/D8Advance).
(4) thermal stability of title complex characterizes
The thermogravimetric analysis of title complex characterizes and shows that its skeleton still can stable existence about near 140 ℃, has higher thermostability, for its further Application and Development as material provides the thermostability assurance, sees Fig. 5.(instrument model: Perkin-ElminDiamond TG/DTA).
The main crystallographic data of table 1 title complex
aR
1＝∑(||F
o|-|F
c||)/∑|F
o|；
bwR
2＝[∑w(|F
o|
2-|F
e|
2)
2/∑w(F
o 2)
2]
1/2
The main bond distance of table 2 title complex
And bond angle [°]
*
*Symmetry code: #1=x ,-y+3/2, z-1/2.
Claims (6)
1. the cadmium complex of xanthene-9-carboxylic acid, it is characterized in that: title complex is the title complex of following chemical formula: [Cd (L)
2(CH
3OH)
2]
∞, L=xanthene-9-carboxyl anion part wherein, the structural formula of L is as follows:
2. the cadmium complex of xanthene according to claim 1-9-carboxylic acid is characterized in that; Described complex crystal belongs to oblique system, and spacer is P2 (1)/c, and unit cell parameters is
α=90 °, β=105.859 (12) °, γ=90 °,
Basic structure is a chain, has a kind of Cd
IISeven coordination environments.
3. the preparation method of the cadmium complex of the described xanthene of claim 1-9-carboxylic acid, it is characterized in that: it comprises the steps: under the room temperature, with part HL dissolve with methanol, adds 2 then, and the 6-lutidine stirs; Add the metal cadmium salt again, the stirring and dissolving after-filtration, gained filtrate is left standstill volatilization and was obtained colourless bulk-shaped monocrystal in 5-8 days, and successively with distilled water, ethanol and ether washing, drying obtains again.
4. the preparation method of the cadmium complex of xanthene according to claim 3-9-carboxylic acid is characterized in that: described part HL is dissolved in the solution of making in the methyl alcohol, and the concentration of part HL is 0.02～0.05molL
-1
5. according to the preparation method of the cadmium complex of claim 3 or 4 described xanthene-9-carboxylic acids, it is characterized in that: the mol ratio of part HL and metal cadmium salt is 1: 1～1: 2.
6. according to the preparation method of the cadmium complex of the described xanthene of claim 5-9-carboxylic acid, it is characterized in that: in the methanol solution of part HL, 2 of adding, the mol ratio of 6-lutidine and part HL is 1: 1～3: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509040A (en) * | 2012-06-26 | 2014-01-15 | 宁波大学 | Coordination polymer with high thermal stability and fluorescence properties and preparation method thereof |
| CN116693868A (en) * | 2023-05-10 | 2023-09-05 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999024527A1 (en) * | 1997-11-07 | 1999-05-20 | Omd Devices Llc | Fluorescent composition for the manufacture of cd-rom type optical memory disks |
| CN101402646A (en) * | 2008-11-14 | 2009-04-08 | 哈尔滨工业大学 | Blue light emitting organic luminescent material pyridine diimine cadmium complex and method of preparing the same |
-
2010
- 2010-09-10 CN CN 201010278223 patent/CN102286008B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999024527A1 (en) * | 1997-11-07 | 1999-05-20 | Omd Devices Llc | Fluorescent composition for the manufacture of cd-rom type optical memory disks |
| CN101402646A (en) * | 2008-11-14 | 2009-04-08 | 哈尔滨工业大学 | Blue light emitting organic luminescent material pyridine diimine cadmium complex and method of preparing the same |
Non-Patent Citations (2)
| Title |
|---|
| JING-CAO DAI 等: "Synthesis, Structure, and Fluorescence of the Novel Cadmium(II)-Trimesate Coordination Polymers with Different Coordination Architectures", 《INORGANIC CHEMISTRY》 * |
| YOSHIE INOMATA 等: "Characterization and crystal structure of cadmium(II) halide complexes with amino acids and their derivatives VI. The comparison of crystal structures of cadmium(II) halide complexes with three kinds of piperidine carboxylic acids", 《JOURNAL OF INORGANIC BIOCHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509040A (en) * | 2012-06-26 | 2014-01-15 | 宁波大学 | Coordination polymer with high thermal stability and fluorescence properties and preparation method thereof |
| CN116693868A (en) * | 2023-05-10 | 2023-09-05 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
| CN116693868B (en) * | 2023-05-10 | 2024-05-10 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
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