CN102153573B - Metal complex of polydentate pyridine ligand, and preparation method and application thereof - Google Patents
Metal complex of polydentate pyridine ligand, and preparation method and application thereof Download PDFInfo
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- CN102153573B CN102153573B CN201110047247A CN201110047247A CN102153573B CN 102153573 B CN102153573 B CN 102153573B CN 201110047247 A CN201110047247 A CN 201110047247A CN 201110047247 A CN201110047247 A CN 201110047247A CN 102153573 B CN102153573 B CN 102153573B
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Abstract
The invention relates to a metal complex of a polydentate pyridine ligand, and a preparation method and application thereof. The metal complex is a cadmium metal complex of a 2,3,6,7,10,11-hexa(2-pyridine) dipyrazine [2,3-f:2',3'-h] quinoxaline ligand; and the method for preparing the complex by a diffusion process comprises the following steps of: putting chloralkane solution in which the 2,3,6,7,10,11-hexa(2-pyridine) dipyrazine [2,3-f:2',3'-h] quinoxaline HPDQ ligand is dissolved on a bottom layer of a test tube at the room temperature; adding mixed solution of nitrile alkane and chloralkane on the upper side of the chloralkane solution; and adding nitrile alkane solution in which metal salts and particularly Cd(NO3)2 are dissolved on the topside layer; and standing a reaction system and diffusing for 20 to 30 days to obtain a saffron yellow blocky monocrystal, namely the metal complex. In the method, the reaction condition is mild, and yield and reproducibility are high. The metal complex can be used as luminescent materials and has the wide prospect.
Description
Technical field
The present invention relates to field of light emitting materials, especially one type 2,3,6; 7,10, the two pyrazines [2 of 11-six (2-pyridine); 3-f:2 ', 3 '-h] quinoxaline (HPDQ) ligand metal title complex and preparation method thereof, it can be used as luminescent material and has broad application prospects.
Background technology
Pl-is the most general is applied as fluorescent lamp.It is the luminescent powder on the ultraviolet ray excited tube wall that geseous discharge produces in the fluorescent tube and send visible light, and its efficient is about 5 times of incandescent light.In addition, the pl-of " black lamp " and other monochromatic lamps can be widely used in printing, duplicates, medical treatment, plant-growth, lures in the technology such as worm and decoration.Pl-can also provide the information of structure, composition and the environment atomic arrangement of some materials; It is a kind of nondestructive, highly sensitive analytical procedure; If in this alanysis method, just can make this alanysis method more be deep into the field of microcell, selective exitation and transient process laser applications, make it further become important research means again; Be applied to fields such as physics, Materials science, chemistry and molecular biology, new frontier branch of science progressively occurs.
Metal complexes is as a kind of novel luminous organic material, owing to it has received people's attention in the potential application of aspects such as optical pickocff and organic luminescent device.D in recent years
10Metal complexes since have novel structure and potential high-performance (as: fluorescence, fractionation by adsorption, electricity lead and catalysis etc.) received people very big concern and by a large amount of synthetic and study; One of focus (S.Leininger is studied in the forward position that also becomes simultaneously coordination chemistry; B.Olenyuk, P.J.Stang, Chem.Rev.2000; 100,853; S.Wang, Coord.Chem.Rev.2001,215,79; O.R.Evans, W.Lin, Acc.Chem.Res.2002,35,5112; P.J.Steel, Acc.Chem.Res.2005,38,243; B.-H.Ye, M.-L.Tong, X.-M.Chen, Coord.Chem.Rev.2005,249,545).Multiple tooth pyridines part has abundant coordination mode; And the multiple tooth pyridines part of big ring that contains big 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 maybe, particularly the aromatics pyridyl ligands aspect luminous by the extensive and a large amount of research of people (as: Z.Y.Xiao; X.Zhao; X.K.Jiang and Z.T.Li, Langmuir, 2010; 26,13048; H.R.Li, W.J.Cheng, Y.Wang, B.Y.Liu, W.J.Zhang, H.J.Zhang, Chem.Eur.J., 2010,16,2125; W.S.Liu, T.Q.Jiao, Y.Z.Li, Q.Z.Liu, M.Y.Tan, H.Wang, L.F.Wang, J.Am.Chem.Soc.2004,126,2280; A.Mitra, A.K.Mittal and C.P.Rao, Chem.Commun., 2010, DOI:10.1039/c0cc04967k; C.Z.Li, K.B.Male, S.Hrapovic and J.H.T.Luong, Chem.Commun., 2005,3924; K.Yea, S.Lee, J.Choo, C.H.Ohand S.Lee, Chem.Commun., 2006,1509; P.W.Du and R.Eisenberg, Chemical Science.2010,1,502; C.Vijayakumar, K.Sugiyasu, M.Takeuchi, Chemical Science.2011,2,291).Therefore, this type of title complex has wide space aspect the further research and development of structure and performance.
The preparation method of the multiple tooth pyridines ligand metal title complex of reporting in the document at present commonly used adopts is compound method such as hydro-thermal, this method exist temperature of reaction high, dangerous big, productive rate is low and technological deficiency such as repeatable difference.
Summary of the invention
The preparation method who the objective of the invention is to solve existing multiple tooth pyridines ligand metal title complex exist temperature of reaction high, dangerous big, productive rate is low and problem such as repeatable difference; Multiple tooth pyridines ligand metal title complex that a kind of reaction conditions is gentle, productive rate is high, reproducibility is good and preparation method thereof is provided, and the application of cadmium metal title complex aspect luminescent material.
Multiple tooth pyridines ligand metal title complex provided by the invention is 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part, chemical formula is: [Cd (NO
3)
2]
4(HPDQ) (H
2O)
8, HPDQ=2 wherein, 3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] quinoxaline.
The crystal of described cadmium metal title complex belongs to oblique system; Spacer is C2/c; Unit cell parameters is a=22.675 (5); B=15.860 (3); C=18.331 (4)
α=90; β=110.86 (3), γ=90 °, V=6160 (2)
The present invention provides the preparation method of above-mentioned multiple tooth pyridines ligand metal title complex simultaneously, and this method comprises the steps:
1st, under the room temperature, will be dissolved with part 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the chloroparaffin solution of quinoxaline HPDQ places the test tube bottom;
2nd, the mixing solutions of adding nitrile alkane and chloroparaffin on the chloroparaffin solution of part HPDQ;
3rd, add again and be dissolved with metal-salt Cd (NO on the upper strata of the 2nd step reaction solution
3)
2The nitrile alkane solution;
4th, at last reaction system is left standstill diffusion and obtained the safran bulk-shaped monocrystal in 20～30 days, be 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part.
The concentration of the chloroparaffin solution of described part HPDQ of the 1st step is 0.01～0.02molL
-1
Described chloroparaffin comprises monochloro methane, methylene dichloride, trichloromethane and 1,2-ethylene dichloride.
The volume ratio of nitrile alkane and chloroparaffin is 1: 1～1: 1.2 in described nitrile alkane of the 2nd step and the chloroparaffin mixing solutions.
Described metal-salt Cd (NO of the 3rd step
3)
2The concentration of nitrile alkane solution be 0.03～0.06molL
-1
Described nitrile alkane comprises acetonitrile, propionitrile and butyronitrile.
Described metal-salt can also be Cu
2I, Zn (NO
3)
2, Mn (NO
3)
2, Ce (NO
3)
3, Pd (NO
3), HgBr
2Or Nd (NO
3)
3
Of the present invention 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part can be used as luminescent material and is applied.
In addition, the part HPDQ that uses among the present invention has good selectivity to partial cation, and its detection method is comparatively simple, and selectivity is higher, can be used as fluorescent probe and is applied at detection range.
Advantage of the present invention and beneficial effect:
The compound method of title complex provided by the invention is different from the d commonly used that reports in the present document
10The compound methods such as hydro-thermal of metal pyridines ligand-complexes, overcome its temperature high, dangerous big, productive rate is low and the technological deficiency of repeatable difference; The compound method that the present invention represents, mild condition, productive rate are high, reproducibility is good; The title complex that the present invention represents can produce fluorescence; Therefore can be used as luminescent material and have broad prospects; Along with luminescent material continuous advancement in technology and fast development, can expect that it provides opportunity to develop not only can for molecular engineering and molecule synthesis; More can improve Energy efficiency, there is significant meaning aspects such as reduction manufacturing cost.
Description of drawings
The Cd coordination environment figure of Fig. 1 title complex and the structural representation of title complex.
Embodiment
Cadmium metal complex crystal of the present invention belongs to oblique system; Spacer is C2/c; Unit cell parameters is a=22.675 (5); B=15.860 (3); C=18.331 (4)
α=90; β=110.86 (3), there are two kinds of different Cd center coordination environments in γ=90 ° in V=6160 (2)
crystalline structure.
In the preparation method of title complex of the present invention, part HPDQ is dissolved in that to process strength of solution in the chloroparaffin be 0.01～0.02molL
-1The volume ratio of the mixing solutions of chloroparaffin and nitrile alkane is 1: 1-1: 1.2; Cadmium nitrate is dissolved in nitrile alkane, and to process the concentration of solution be 0.03～0.06molL
-1The mol ratio of part HPDQ and metal-salt is 1: 3; The volume ratio of upper, middle and lower-ranking solution is 1: 3: 1～1: 4: 1.
Embodiment 1: the preparation of title complex
0.05mmol HPDQ is placed the test tube bottom, with the dissolving of 3mL methylene dichloride, the middle mixed solution 15ml that adds 1: 1 volume ratio of methylene dichloride/acetonitrile; 0.15mmol Cd (NO
3)
26H
2O with the dissolving of 3mL acetonitrile, places the test tube upper strata.Sealing and standing 25 days, the safran bulk-shaped monocrystal appears in the place, boundary that connects of solution interface on the test tube wall, is described d
10Metal pyridines ligand-complexes, or claim 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part.
Embodiment 2: the preparation of title complex
0.03mmol HPDQ is placed the test tube bottom, with the dissolving of 3mL trichloromethane, the middle mixed solution 15ml that adds 1: 11 volume ratio of trichloromethane/acetonitrile; 0.09mmol Cd (NO
3)
26H
2O with the dissolving of 3mL acetonitrile, places the test tube upper strata.Sealing and standing 25 days, the safran bulk-shaped monocrystal appears in the place, boundary that connects of solution interface on the test tube wall, is described d
10Metal pyridines ligand-complexes, or claim 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part.
Embodiment 3: the preparation of title complex
0.06mmol HPDQ is placed the test tube bottom, use 3mL1, the dissolving of 2-ethylene dichloride, middle adding 1, the mixed solution 15ml of 1: 1.2 volume ratio of 2-ethylene dichloride/propionitrile; 0.18mmol Cd (NO
3)
26H
2O with the dissolving of 3mL propionitrile, places the test tube upper strata.Sealing and standing 25 days, the safran bulk-shaped monocrystal appears in the place, boundary that connects of solution interface on the test tube wall, is described d
10Metal pyridines ligand-complexes, or claim 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part.
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.On the SCX-Mini single crystal diffractometer, use Mo-K through the graphite monochromator monochromatization
αRay (λ=0.71073
), with
Mode is collected diffraction data.Carry out reduction of data with Bruker SAINT program.The diffraction data of part-structure carries out absorption correction with the SADABS program.Crystalline structure is by synthetic the solving of direct method combination difference Fourier.All non-hydrogen atom coordinate and anisotropic parameters carry out the complete matrix least-squares refinement, and the Wasserstoffatoms position is confirmed by theoretical mode computation.Detailed axonometry data are seen table 1.Structure is seen Fig. 1.Fig. 1 is the Cd coordination environment figure of cadmium complex and the structural representation of title complex;
The main crystallographic data of table 1 cadmium complex.
aR＝∑(‖F
0|-|F
C‖)/∑|F
0|；
bwR＝[∑w(|F
0|
2-|F
C|
2)
2/∑w(F
0 2)]
1/2
Claims (8)
1. a multiple tooth pyridines ligand metal title complex is characterized in that described metal complexes is 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part, chemical formula is: [Cd (NO
3)
2]
4(HPDQ) (H
2O)
8, HPDQ=2 wherein, 3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] quinoxaline.
2. multiple tooth pyridines ligand metal title complex according to claim 1; The crystal that it is characterized in that described cadmium metal title complex belongs to oblique system; Spacer is C2/c; Unit cell parameters is a=22.675 (5); B=15.860 (3);
α=90; β=110.86 (3); γ=90 °,
3. the preparation method of the described multiple tooth pyridines ligand metal title complex of claim 1 is characterized in that this method comprises the steps:
1st, under the room temperature, will be dissolved with part 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the chloroparaffin solution of quinoxaline HPDQ places the test tube bottom; Described chloroparaffin is a methylene dichloride, trichloromethane or 1,2-ethylene dichloride;
2nd, the mixing solutions of adding nitrile alkane and chloroparaffin on the chloroparaffin solution of part HPDQ; Described nitrile alkane is acetonitrile or propionitrile;
3rd, add again and be dissolved with metal-salt Cd (NO on the upper strata of the 2nd step reaction solution
3)
2The nitrile alkane solution;
4th, at last reaction system is left standstill diffusion and obtained the safran bulk-shaped monocrystal in 20～30 days, be 2,3,6,7,10, the two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part.
4. method according to claim 3 is characterized in that the concentration of the chloroparaffin solution of described part HPDQ of the 1st step is 0.01～0.02mol L
-1
5. method according to claim 3 is characterized in that the volume ratio of nitrile alkane and chloroparaffin is 1: 1～1: 1.2 in the 2nd step described nitrile alkane and the chloroparaffin mixing solutions.
6. method according to claim 3 is characterized in that described metal-salt Cd (NO of the 3rd step
3)
2The concentration of nitrile alkane solution be 0.03～0.06mol L-1.
7. method according to claim 3, the mol ratio that it is characterized in that HPDQ and metal-salt is 1: 3.
8. the application of the described multiple tooth pyridines ligand metal title complex of claim 1 is characterized in that described 2,3; 6,7,10; The two pyrazines of 11-six (2-pyridine) [2,3-f:2 ', 3 '-h] the cadmium metal title complex of quinoxaline part can be used as luminescent material and is applied.
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