CN108424527B - Synthetic method of Zn (II) complex of three-dimensional mixed ligand and application of fluorescent probe - Google Patents
Synthetic method of Zn (II) complex of three-dimensional mixed ligand and application of fluorescent probe Download PDFInfo
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Abstract
The invention discloses a synthetic method of a Zn (II) complex of a three-dimensional mixed ligand and application of a fluorescent probe, wherein the Zn (II) complex has a chemical formula of [ Zn (II) ]2(TRZ)2(DBTDC‑O2)]DMAc, wherein said DMAc is N, N-dimethylacetamide and said DBTDC-O2The 3,7- (5, 5-dibenzothiophene dioxide) dicarboxylic acid with deprotonated carboxyl is prepared by the preparation method, the preparation method is simple and easy to operate, the required equipment is simple, the reproducibility is good, and the prepared complex has the advantages of high yield, good stability and the like, and can be widely applied to the field of fluorescent crystal materials.
Description
Technical Field
The invention belongs to the technical field of porous metal-organic coordination compounds, and particularly relates to a synthesis method of a Zn (II) complex of a three-dimensional mixed ligand and application of a fluorescent probe.
Background
The metal-organic coordination polymer is obtained by coordination crystallization of metal ions/metal clusters and organic ligands containing nitrogen and oxygen elements. The novel organic-inorganic hybrid crystal material not only has rich structure and topology, but also has the characteristics superior to other traditional materials in a plurality of fields, so that the novel organic-inorganic hybrid crystal material has potential application prospects in the fields of catalysis, optical devices, fluorescence, gas storage, separation, ion exchange and the like, and further becomes the most active functional material for research in the fields of coordination chemistry and materials in recent years (B.Moulton, M.J.Zawootko, chem.Rev.,2001,101,1629-1658; C.D.Wu, W.Lin, Angew.chem., Int.Ed.,2005,44, 1958-1961; W.P.Lustig, S.Mukherjee, N.D.dd, A.V.Desai, J.Li, S.K.Ghosh, chem.Soc.Rev.,2017,46, 3242-3285). Generally, metal-organic coordination polymers constructed by general metal ions (zinc, cadmium and the like) and organic ligands generally retain the inherent fluorescence property of the organic ligands, and can generate a plurality of optical properties such as fluorescence detection, so that the metal-organic coordination polymers attract attention and favor of relevant researchers worldwide (J.C.G.Bznli, C.Piguet, chem.Soc.Rev.,2005,34, 1048-1077; J.G.Mao, Coord.chem.Rev.,2007,251,1493-1520; S.Mohapatra, K.P.S.S.Hembram, U.Waghmare, T.K.Maji, chem.Mater, 21, 5406-5412; M.D.Alledorf, C.A.Bauer, R.K.Bhakukta, R.J.T.Ho.2009, Sov-1352, 2).
However, metal-organic coordination polymer materials tend to be very limited in their application due to poor stability, especially in aqueous solutions. Many scientists have attempted to improve the water stability of materials using multiple node linkages, introduction of hydrophobic groups, surface hydrophobic functionalization, and other methods. However, there are few reports on materials having water stability and excellent detection effect. To date, no water-stable fluorescent polymer material constructed based on a mixture of organic ligands, 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid and 1,2, 4-triazole (HTRZ), has been reported. The related research will certainly deepen the understanding of the relationship between the structure and the optical performance of the mixed-metal fluorescent microporous material, so as to select the luminescent and detecting material with novel structure and excellent performance. Has very important significance in the fields of crystallography and luminescent materials.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a Zn (II) complex constructed based on a mixed ligand of 3,7- (5, 5-dibenzothiophene dioxide) dicarboxylic acid and 1,2, 4-triazole, wherein the 3,7- (5, 5-dibenzothiophene dioxide) dicarboxylic acid is one of rigid organic ligands with a good pi-type conjugated system, and the deprotonated 3,7- (5, 5-dibenzothiophene dioxide) dicarboxylic acid and 1,2, 4-triazole have excellent coordination capacity.
It is another object of the present invention to provide a process for preparing the above Zn (II) complex,
the invention also aims to provide the application of the Zn (II) complex as a fluorescent probe in the detection of nitrofurantoin.
The purpose of the invention is realized by the following technical scheme.
Zn (II) complex constructed based on 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid and 1,2, 4-triazole mixed ligand, wherein the chemical formula of the Zn (II) complex is [ Zn (II) ]2(TRZ)2(DBTDC-O2)]DMAc, wherein said DMAc is N, N-dimethylacetamide and said DBTDC-O23,7- (5, 5-Bisbenzobenzothiophene dioxide) dicarboxylic acid deprotonated to the carboxyl group, DBTDC-O2The structural simple formula of (1) is as follows:
TRZ is deprotonated 1,2, 4-triazole, and TRZ has a structural formula:
in the above technical scheme, the Zn (II) complex belongs to a tetragonal system, the space group is P-42(1)/c, and the unit cell parameters are
α＝90.00°,β＝90.00°,γ＝90.00°,
Z＝8。
In the above technical solution, the basic structural unit of the zn (ii) complex includes: one crystallographically independent Zn1, one crystallographyIndependent Zn2, two TRZ and one DBTDC-O2，
The DBTDC-O2Both oxygen O5 and O6 of one carboxyl group are linked to the Zn 1;
the DBTDC-O2One oxygen O1 of the other carboxyl group is linked to the Zn2, the Zn2 is linked to N1 and N4, the N1 and N4 are each from the nitrogen of one of the TRZ;
one DMAc is present as a free guest molecule in the framework of the zn (ii) complex.
The preparation method of the Zn (II) complex comprises the following steps:
adding a mixed solvent into 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid, 1,2, 4-triazole and zinc (II) metal salt, uniformly dispersing the mixed solvent in the mixed solvent, keeping the temperature at 85-110 ℃ for 3-5 days, then cooling to room temperature, filtering to obtain colorless massive single crystals which are the Zn (II) complex, wherein,
the ratio of the 3,7- (5, 5-dibenzothiophene dioxide) dicarboxylic acid to the 1,2, 4-triazole to the zinc (II) metal salt is (0.22-0.24) according to the mass: 1: 1,
the mixed solvent is a mixture of N, N-dimethylacetamide, methanol and water, and the volume part ratio of the N, N-dimethylacetamide to the methanol to the water is (1.5-3): (1-2): (1.5 to 3) of a surfactant,
the ratio of the volume parts of the N, N-dimethylacetamide to the mass parts of the zinc (II) metal salt is (13-15): 1.
in the technical scheme, the colorless massive single crystal obtained after filtration is washed and dried.
In the technical scheme, the temperature for 3-5 days is 90-100 ℃.
In the above technical scheme, the unit of one volume part is mL, and the unit of one quantity part of the substance is mmol.
In the above technical scheme, the cooling to room temperature is natural cooling.
The Zn (II) complex is used as a fluorescent probe for detecting nitrofurantoin.
Ultrasonically dispersing a Zn (II) complex in water containing nitrofurantoin, and exciting by using ultraviolet rays, wherein the Zn (II) complex is subjected to fluorescence quenching.
Compared with the prior art, the preparation method provided by the invention is simple and easy to operate, the required equipment is simple, the reproducibility is good, and the prepared complex has the advantages of high yield, good stability and the like, and can be widely applied to the field of fluorescent crystal materials.
Drawings
FIG. 1 is a diagram showing the coordination environment of a Zn (II) complex of the present invention;
FIG. 2 is a three-dimensional structural view of a Zn (II) complex of the present invention;
FIG. 3 is a solid state fluorescence spectrum of a Zn (II) complex according to the present invention;
FIG. 4 is a graph of X-ray powder diffraction (PXRD) experiment, theory and two-day standing in water for a Zn (II) complex of the present invention;
FIG. 5 is a thermogravimetric analysis plot of a Zn (II) complex of the present invention;
FIG. 6 is a carbon dioxide adsorption curve of a Zn (II) complex of the present invention;
FIG. 7 is a graph showing fluorescence quenching of a Zn (II) complex of the present invention in an aqueous solution with respect to the antibiotic Nitrofurantoin (NFT).
Detailed Description
1,2, 4-triazole (98%) and zinc nitrate hexahydrate (98%) used in the course of the experiment were purchased from Sigma-Aldrich Sigma Aldrich trade company, N, N-dimethylacetamide (analytical grade), methylene chloride (analytical grade) and methanol (analytical grade) from Merrel chemical technology company, Inc. of Shanghai. All drugs and reagents were used directly without further purification.
The technical scheme of the invention is further explained by combining specific examples.
Example 1
The preparation method of the Zn (II) complex comprises the following steps:
3,7- (5, 5-dibenzo-p-phenylene oxide) dicarboxylic acid, 1,2, 4-triazole and Zn (NO)3)2·6H2O additionAdding a mixed solvent into a beaker, uniformly dispersing substances in the beaker in the mixed solvent, stirring for 30 minutes at room temperature to obtain a clear solution, sealing the obtained clear solution into a hydrothermal reaction kettle (made of stainless steel), keeping the hydrothermal reaction kettle in an oven at 90 ℃ for 5 days (24 hours per day, keeping the temperature unchanged), naturally cooling to the room temperature of 20-25 ℃, filtering to obtain a colorless massive single crystal Zn (II) complex, washing the colorless massive single crystal by using N, N-dimethylformamide, drying in the air for 1 day, wherein the yield is 67 percent,
the amount of 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid was 0.023mmol, the amount of 1,2, 4-triazole was 0.1mmol, and Zn (NO) was added3)2·6H2The amount of O substance was 0.1mmol, the mixed solvent was a mixture of N, N-dimethylacetamide, methanol and water, the volume of N, N-dimethylacetamide was 1.5mL, the volume of methanol was 1mL, and the volume of water was 1.5 mL.
Example 1 the main infrared absorption peaks of the prepared zn (ii) complex are: 3436br,1303s,1173s,1130s,1090s,1006s,883s,777s,665s,591s,522s,437 s; the elemental analysis result is as follows: theoretical value C, 40.18; h, 3.20; n, 14.92%, the experimental value is C, 40.12; h, 3.15; n,14.79 percent.
Example 2
The preparation method of the Zn (II) complex comprises the following steps:
3,7- (5, 5-dibenzo-p-phenylene oxide) dicarboxylic acid, 1,2, 4-triazole and Zn (NO)3)2·6H2Adding O into a beaker, adding a mixed solvent into the beaker, uniformly dispersing substances in the beaker in the mixed solvent, stirring for 30 minutes at room temperature to obtain a clear solution, sealing the obtained clear solution into a hydrothermal reaction kettle (made of stainless steel), keeping the hydrothermal reaction kettle in an oven at 90 ℃ for 4 days, naturally cooling to the room temperature of 20-25 ℃, filtering to obtain a colorless blocky monocrystal, namely Zn (II) complex, washing the colorless blocky monocrystal by using N, N-dimethylformamide, drying in the air for 1 day, wherein the yield is 65%,
the amount of the 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid was 0.035mmol, the amount of the 1,2, 4-triazoleIn an amount of 0.15mmol, Zn (NO)3)2·6H2The amount of O substance was 0.15mmol, the mixed solvent was a mixture of N, N-dimethylacetamide, methanol and water, the volume of N, N-dimethylacetamide was 2mL, the volume of methanol was 1.3mL, and the volume of water was 2 mL.
Example 2 the main infrared absorption peaks of the prepared zn (ii) complex are: 3435br,1303s,1173s,1130s,1091s,1005s,883s,777s,665s,592s,522s,436 s; the elemental analysis result is as follows: theoretical value C, 40.18; h, 3.20; n, 14.92%, the experimental value is C, 40.16; h, 3.17; n,14.81 percent.
Example 3
The preparation method of the Zn (II) complex comprises the following steps:
3,7- (5, 5-dibenzo-p-phenylene oxide) dicarboxylic acid, 1,2, 4-triazole and Zn (NO)3)2·6H2Adding O into a beaker, adding a mixed solvent into the beaker, uniformly dispersing substances in the beaker in the mixed solvent, stirring for 30 minutes at room temperature to obtain a clear solution, sealing the obtained clear solution into a hydrothermal reaction kettle (made of stainless steel), keeping the hydrothermal reaction kettle in an oven at 95 ℃ for 5 days, naturally cooling to the room temperature of 20-25 ℃, filtering to obtain a colorless blocky monocrystal, namely Zn (II) complex, washing the colorless blocky monocrystal by using N, N-dimethylformamide, drying in the air for 1 day, wherein the yield is 68 percent,
the amount of 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid, 1,2, 4-triazole and Zn (NO) were 0.04mmol, 0.175mmol, respectively3)2·6H2The amount of O substance was 0.175mmol, the mixed solvent was a mixture of N, N-dimethylacetamide, methanol and water, the volume of N, N-dimethylacetamide was 2.5mL, the volume of methanol was 1.6mL, and the volume of water was 2.5 mL.
Example 3 the main infrared absorption peaks of the prepared zn (ii) complex are: 3434br,1302s,1173s,1131s,1091s,1005s,884s,777s,664s,592s,523s,435 s; the elemental analysis result is as follows: theoretical value C, 40.18; h, 3.20; n, 14.92%, experimental value C, 40.17; h, 3.19; n,14.91 percent.
Example 4
The preparation method of the Zn (II) complex comprises the following steps:
3,7- (5, 5-dibenzo-p-phenylene oxide) dicarboxylic acid, 1,2, 4-triazole and Zn (NO)3)2·6H2Adding O into a beaker, adding a mixed solvent into the beaker, uniformly dispersing substances in the beaker in the mixed solvent, stirring for 30 minutes at room temperature to obtain a clear solution, sealing the obtained clear solution into a hydrothermal reaction kettle (made of stainless steel), keeping the hydrothermal reaction kettle in an oven at 100 ℃ for 6 days, naturally cooling to the room temperature of 20-25 ℃, filtering to obtain a colorless blocky monocrystal, namely Zn (II) complex, washing the colorless blocky monocrystal by using N, N-dimethylformamide, drying in the air for 1 day, wherein the yield is 69 percent,
the amount of 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid was 0.045mmol, the amount of 1,2, 4-triazole was 0.2mmol, and Zn (NO)3)2·6H2The amount of O substance was 0.2mmol, the mixed solvent was a mixture of N, N-dimethylacetamide, methanol and water, the volume of N, N-dimethylacetamide was 3mL, the volume of methanol was 2mL, and the volume of water was 3 mL.
Example 4 the main infrared absorption peaks of the prepared zn (ii) complex are: 3436br,1302s,1173s,1131s,1090s,1006s,883s,778s,665s,593s,522s,435 s; the elemental analysis result is as follows: theoretical value C, 40.18; h, 3.20; n, 14.92%, the experimental value is C, 40.10; h, 3.19; n,14.85 percent.
The Zn (II) complexes obtained in examples 1 to 4 are further characterized as follows:
(1) determination of Crystal Structure
Selecting single crystal with proper size under microscope, and monochromating Mo-Ka ray with graphite at room temperature on Bruker APEX II CCD diffractometer
To be provided with
The diffraction data is collected. All diffraction data were performed by SADABS software using the multi-scan methodSemi-empirical absorption correction. The unit cell parameters were determined using the least squares method. Data reduction and structure resolution were done using SAINT and SHELXL packages, respectively. All non-hydrogen atoms were anisotropically refined using full matrix least squares. Detailed crystal determination data of the Zn (II) complex prepared in example 1 are shown in Table 1, and the crystal structure is shown in FIGS. 1 and 2.
TABLE 1 Main crystallographic data and refinement parameters of the crystalline materials prepared
aR1＝Σ(||Fo|-|Fc||)/Σ|Fo|.bwR2＝[Σw(|Fo|2-|Fc|2)2/Σw(Fo 2)2]1/2
As can be seen from the above characterization results, the complex crystal of the invention belongs to the tetragonal system, the space group is P-42(1)/c, and the unit cell parameter is
α＝90.00°,β＝90.00°,γ＝90.00°,
And Z is 8. As shown in figure 1, the asymmetric structural unit of the material comprises a crystallographically independent Zn1, a crystallographically independent Zn2, a deprotonated 1,2, 4-triazole anion and a completely deprotonated 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid anion. Zn1 links O5 and O6 from the carboxyl functional group of the organic ligand; meanwhile, Zn2 is linked with N1 and N2 from two different 1,2, 4-triazole anions and one anion from 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acidO1 of (1). Zn1 and Zn2 are connected with each other through the two organic ligands to obtain a three-dimensional microporous structure (figure 2).
(2) Study of solid fluorescence properties of complexes
25mg of the Zn (II) complex prepared in example 1 was ground, tableted and molded, and placed in a Cary Eclipse fluorescence spectrometer, and the emission peak with the maximum emission wavelength of 392nm was obtained by testing at room temperature using an excitation wavelength of 327nm, as shown in FIG. 3.
(3) Powder diffraction measurement
Powder diffraction data were collected and measured on a Bruker D8 ADVANCE diffractometer. The instrument operating voltage was 40kV and the current was 40 mA. A graphite monochromatized Cu target X-ray was used. The width of the divergent slit is 0.6mm, the width of the anti-divergent slit is 6mm, and the Soller slit is 4 degrees; data collection was done using a 2 theta/theta scan pattern with continuous scans in the range of 5 deg. to 40 deg., at a scan rate of 0.1 deg./sec, with a step size of 0.01 deg.. The results of the powder X-ray diffraction of the theoretical simulation were obtained by performing a simulation of the X-ray single crystal structure using the Mercury 1.4.1 software package. As shown in fig. 4, the powder diffraction result of the zn (ii) complex prepared in example 1 shows that the powder diffraction peak (experimental pattern) of the macro-prepared crystalline product is the same as the theoretically simulated diffraction pattern, indicating that it has reliable phase purity and consistency with the crystal structure. Meanwhile, the crystal structure can be kept after standing in water for two days, so that the fluorescent material has excellent water stability and provides guarantee for the application of the fluorescent material.
(4) Thermogravimetric analysis determination
The thermogravimetric analysis experiments were performed on a thermogravimetric analyzer of Shimadzu simultaneous DTG-60A, measured by heating from room temperature to 800 ℃ at a rate of 10 ℃/min in air. The measurement results show that the three-dimensional framework of the Zn (II) complex prepared in example 1 can stably exist before 410 ℃. As shown in FIG. 5, as the temperature continues to rise, the skeleton of the complex begins to decompose, leaving a residue of metal oxide.
(5) Gas adsorption assay
Carbon dioxide adsorption data were measured on a U.S. mike instrument ASAP 2020 series specific surface meter.100mg of the Zn (II) complex prepared in example 1 was placed in 20mL of dichloromethane for 3 days, the dichloromethane solvent was replaced every 12 hours, and an activated sample was obtained after 5 hours of activation at 100 ℃. And the carbon dioxide adsorption amount of the test material (sample after activation) at a temperature of 195K under a pressure of 0-1 atmosphere is calculated to be 289m for the specific surface area of the material by using BET and Langmuir models as shown in FIG. 62 g-1And 385m2 g-1。
(6) Study of solid fluorescence properties of complexes
1mg of the Zn (II) complex prepared in example 1 was ultrasonically dispersed in 3mL of water after grinding, two portions were made in parallel, 1mmol of nitrofurantoin was added to one portion, the mixture was placed in a Cary Eclipse fluorescence spectrometer and tested at an excitation wavelength of 327nm, and a sample without the addition of a nitrofurantoin solution gave an emission wavelength of 392nm (aqueous solution curve in the figure), and fluorescence quenching occurred in the sample with the addition of the nitrofurantoin solution. Therefore, the Zn (II) complex has obvious fluorescence quenching effect on the specific antibiotic Nitrofurantoin (NFT), and can be used as a fluorescent probe for detecting the nitrofurantoin to fill the blank in the field at home and abroad.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (8)
1. A Zn (II) complex constructed based on a mixed ligand of 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid and 1,2, 4-triazole, characterized in that the chemical formula of the Zn (II) complex is [ Zn ]2(TRZ)2(DBTDC-O2)]DMAc, wherein said DMAc is N, N-dimethylacetamide and said DBTDC-O23,7- (5, 5-Bisbenzobenzothiophene dioxide) dicarboxylic acid deprotonated to the carboxyl group, DBTDC-O2The structural simple formula of (1) is as follows:
TRZ is deprotonated 1,2, 4-triazole, and TRZ has a structural formula:
the crystallographic data and refinement parameters of the Zn (II) complex are:
2. zn (II) complex according to claim 1, characterized in that the basic building block of the Zn (II) complex comprises: one crystallographically independent Zn1, one crystallographically independent Zn2, two TRZ, and one DBTDC-O2，
The DBTDC-O2Both oxygen O5 and O6 of one carboxyl group are linked to the Zn 1;
the DBTDC-O2One oxygen O1 of the other carboxyl group is linked to the Zn2, the Zn2 is linked to N1 and N4, the N1 and N4 are each from the nitrogen of one of the TRZ;
one DMAc is present as a free guest molecule in the framework of the zn (ii) complex.
3. The method for preparing a Zn (II) complex as set forth in any one of claims 1 to 2, comprising the steps of:
adding a mixed solvent into 3,7- (5, 5-dibenzobenzothiophene dioxide) dicarboxylic acid, 1,2, 4-triazole and zinc (II) metal salt, uniformly dispersing the mixed solvent in the mixed solvent, keeping the temperature at 85-110 ℃ for 3-5 days, then cooling to room temperature, filtering to obtain colorless massive single crystals which are the Zn (II) complex, wherein,
the ratio of the 3,7- (5, 5-dibenzothiophene dioxide) dicarboxylic acid to the 1,2, 4-triazole to the zinc (II) metal salt is (0.22-0.24) according to the mass: 1: 1,
the mixed solvent is a mixture of N, N-dimethylacetamide, methanol and water, and the volume part ratio of the N, N-dimethylacetamide to the methanol to the water is (1.5-3): (1-2): (1.5 to 3) of a surfactant,
the ratio of the volume parts of the N, N-dimethylacetamide to the mass parts of the zinc (II) metal salt is (13-15): 1; the volume parts are in units of mL, and the quantity parts of the substances are in units of mmol.
4. The production method according to claim 3, wherein the colorless bulk single crystal obtained after filtration is subjected to washing and drying treatment.
5. The method according to claim 4, wherein the temperature for 3 to 5 days is 90 to 100 ℃.
6. The method of claim 5, wherein the cooling to room temperature is natural cooling.
7. Use of the Zn (II) complex as defined in any one of claims 1 to 2 as a fluorescent probe for the detection of nitrofurantoin.
8. The use of claim 7, wherein the Zn (II) complex is ultrasonically dispersed in nitrofurantoin-containing water and excited with ultraviolet light, whereby the Zn (II) complex undergoes fluorescence quenching.
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| CN103130838A (en) * | 2013-01-11 | 2013-06-05 | 天津师范大学 | Metal-organic frame porous material based on triazole ligand, and preparation method and application thereof |
| CN103936773A (en) * | 2014-04-08 | 2014-07-23 | 陕西师范大学 | 1, 4-terephthalic acid-regulated polyazole coordination polymer and preparation method thereof |
| CN107880277A (en) * | 2017-12-05 | 2018-04-06 | 池州学院 | A kind of two-dimentional zinc coordination polymer and preparation method thereof |
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| CN103130838A (en) * | 2013-01-11 | 2013-06-05 | 天津师范大学 | Metal-organic frame porous material based on triazole ligand, and preparation method and application thereof |
| CN103936773A (en) * | 2014-04-08 | 2014-07-23 | 陕西师范大学 | 1, 4-terephthalic acid-regulated polyazole coordination polymer and preparation method thereof |
| CN107880277A (en) * | 2017-12-05 | 2018-04-06 | 池州学院 | A kind of two-dimentional zinc coordination polymer and preparation method thereof |
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| Two new metal–triazole-benzenedicarboxylate frameworks affording an uncommon 3,4-connected net and unique 4,6-connected rod packing: hydrothermal synthesis, structure, thermostability and luminescence studies;Luo F. et al.;《CrystEngComm》;20090213;第11卷;第1097-1102页 * |
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