CN105481885A - Synthesis and application of organic-inorganic hybridized Cu (II) complex based on silicotungstic acid - Google Patents
Synthesis and application of organic-inorganic hybridized Cu (II) complex based on silicotungstic acid Download PDFInfo
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- CN105481885A CN105481885A CN201610034076.5A CN201610034076A CN105481885A CN 105481885 A CN105481885 A CN 105481885A CN 201610034076 A CN201610034076 A CN 201610034076A CN 105481885 A CN105481885 A CN 105481885A
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- phenanthroline
- silicotungstic acid
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- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- KCALAFIVPCAXJI-UHFFFAOYSA-N 1,10-phenanthroline-5,6-dione Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CN=C3C2=N1 KCALAFIVPCAXJI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001228 spectrum Methods 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002835 absorbance Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 7
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 239000011365 complex material Substances 0.000 abstract description 2
- 150000004696 coordination complex Chemical class 0.000 abstract description 2
- 238000000295 emission spectrum Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 17
- 238000000034 method Methods 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000863856 Homo sapiens Shiftless antiviral inhibitor of ribosomal frameshifting protein Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses synthesis of an organic-inorganic hybridized Cu (II) complex based on 1,10-phenanthroline-5,6-dione and silicotungstic acid and a photoluminescence application. Metal complex materials have metal centers and organic parts which can both cause luminescence, and those photoluminescence materials are focused due to potential application value in aspects of light-emitting diodes, solar cells, biomedical images and the like. Test results indicate that the hybridized Cu (II) complex based on the 1,10-phenanthroline-5,6-dione and the silicotungstic acid can emit green light emission spectrum and has broad application prospect in organic-inorganic hybridized photoluminescence materials.
Description
Statement about subsidizing research or exploitation: the present invention carries out under the subsidy of the institute-level scientific research main project (GrantNo.2015zd03) of institution of higher education of Henan Province key research project (GrantNo.16B150015) and Hua Rui institute of Xinyang Normal College.
Technical field
The invention belongs to organic water thermal synthesis and Organometallic Chemistry technical field, relate to based on 1,10-phenanthroline-5, the Hydrothermal Synthesis of Cu (II) title complex of the hybrid inorganic-organic of 6-diketone and α-Keggin silicotungstic acid and its fluorescence property, based on organic ligand 1 in particular, the Cu(II of 10-phenanthroline-5,6-diketone and inorganic origin α-Keggin silicotungstic acid) Hydrothermal Synthesis of title complex and the application in hybrid inorganic-organic optical material thereof.
Background technology
The interest of a lot of people has been attracted, especially α-Keggin-type silicotungstic acid based on clustering of polyoxometallate.Organic ligand is selected can provide the relevant report of the 1,10-Phenanthroline-5,6-Quinone of complexible atom N and O atom less.On the other hand, based on the research of poly-metal deoxide, particularly α-Keggin-type silicotungstic acid, because it is applied in catalysis widely, electrochemistry, photochemistry, magnetic, and biochemical performance is paid close attention to widely.Therefore select silicotungstic acid to be inorganic origin, 1,10-Phenanthroline-5,6-Quinone be that organic origin synthesis is containing the title complex of Cu (II).
Summary of the invention
One object of the present invention discloses [Cu (Do)
2(H
2o)]
2(SiW
12o
40) (1) title complex.
Another object of the present invention discloses the preparation method of title complex (1) crystal, the research of take off data and data.
Further object of the present invention discloses the preparation of Cu (II) title complex of the hybrid inorganic-organic based on 1,10-Phenanthroline-5,6-Quinone and α-Keggin silicotungstic acid with zero-dimension structural.
Further object of the present invention discloses the [Cu (Do) with zero-dimension structural
2(H
2o)]
2(SiW
12o
40) (1) title complex in hybrid inorganic-organic optical material, particularly green fluorescence source material aspect.Owing to having metal center, organic moiety, inorganic part, the transition of the electric charge between metal-organic, the guest molecule in coordination compound all may cause luminescence.There are huge potentiality and be concerned in the application of these materials in fluorescent optical sensor, photoluminescence, photic catalysis, display, photodiode, biological medicine image etc.
For achieving the above object, the invention provides following technical scheme:
Have the compound of certain skeleton construction, this compound is new, does not have bibliographical information by CCDC data base querying; Its chemical general formula is as follows:
[Cu(Do)
2(H
2O)]
2(SiW
12O
40)(1)；
The structural formula of Do is that Fig. 1, Do refer to 1,10-Phenanthroline-5,6-Quinone part.
Title complex [Cu (Do)
2(H
2o)]
2(SiW
12o
40) molecular formula of (1) is Fig. 2.
The present invention further discloses Cu (II) complex monocrystal with zero-dimension structural, the related data of crystal is wherein measured by RigakuRAXIS-RAPIDX-ray single crystal diffraction instrument, adopt the MoK α radiation (λ=0.071073nm) of graphite monochromator as diffraction light sources, at the temperature of 293 (2) K, with ω-2 θ scan mode, measure predominant crystal data as follows:
| Molecular formula | Cu 2C 48H 28N 8O 50SiW 12 |
| Molecular weight | 3878.15 |
| Crystallographic system | Othorhombic |
| Spacer | Pbca |
| Length of side a/[nm] | 15.5453(10) |
| Side length b/[nm] | 21.3948(15) |
| Length of side c/[nm] | 22.0731(15) |
| Angle [alpha]/[] | 90 |
| Angle beta/[] | 90 |
| Angle γ/[] | 90 |
| Volume V/[nm 3] | 7341.3(9) |
| Molecules in unit cell | 4 |
| Density [g m –3] | 3.509 |
| Specific absorbance [mm –1] | 19.409 |
| The consistent factor R of point diffraction 1, WR 2[I＞2σ(I)] | 0.0800, 0.1600 |
| Weighting factor GOF (F 2) | 1.271 |
The present invention further discloses the synthetic method of Cu (II) complex monocrystal with zero-dimension structural, it is characterized in that: precision takes Gerhardite 0.0241g (0.1mmol), 1,10-phenanthroline-5,6-diketone 0.0204g (0.1mmol), and hydration silicotungstic acid 0.2159g (0.075mmol), after 12mL water dissolution, be transferred in the teflon-lined reactor of 20mL, keep three days at 150 DEG C, with 6 DEG C/min of slow coolings, obtain green transparent crystal.
Accompanying drawing illustrates:
Fig. 1 is the chemical formula of 1,10-Phenanthroline-5,6-Quinone;
Fig. 2 is the chemical formula of title complex (1);
Fig. 3 is the molecular structure of title complex (1);
Fig. 4 has Cu (II) title complex Solid fluorescene spectrum figure (Solid fluorescene spectrum wavelength is within the scope of 492-577nm green light source) of green emission spectrum.
Embodiment
In order to simple and clearly object, the hereafter appropriate description eliminating known technology, in order to avoid the description of those unnecessary details impact to the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, what be illustrated especially is, prepare the initial substance Gerhardite of the compounds of this invention, hydration silicotungstic acid and 10-phenanthroline-5,6-diketone, all can commercially or easily be obtained (reagent prepared used by the compounds of this invention all derives from business and buys, and rank is analytical pure) by known method.
Embodiment 1
Reference example 1
The structural formula of Do is that Fig. 1, Do refer to 1,10-Phenanthroline-5,6-Quinone part.
Preparation method: add the 110ml vitriol oil in round-bottomed flask, and 1, the 10-phenanthroline in batches adding 15g, add 23g Potassium Bromide simultaneously in batches, separatory drips 55ml concentrated nitric acid, controls temperature of reaction at about 120 DEG C, isothermal reaction 4 hours, remove condensation, discharge bromine gas, obtain yellow powder with after recrystallizing methanol, be 1,10-phenanthroline-5,6-diketone.Reference: YamadaY., SakuraiH., MiyashitaY., FujisawaK., OkamotoK., Polyhedron, 2002,21,2143.
Preparation embodiment 1
150 DEG C of Hydrothermal Synthesiss of title complex (1)
Precision takes Gerhardite 0.0241g (0.1mmol), 1,10-phenanthroline-5,6-diketone 0.0204g (0.1mmol), and hydration silicotungstic acid 0.2159g (0.075mmol), after 12mL water dissolution, be transferred in the teflon-lined reactor of 20mL, keep three days at 150 DEG C, with 6 DEG C/min of slow coolings, obtain green transparent crystal.
Results of elemental analyses, experimental value (%): C, 15.10; H, 0.68; N, 2.72; According to Cu
2c
48h
28n
8o
50siW
12the theoretical value (%) calculated: C, 14.87; H, 0.73; N, 2.89.
FT-IR(KBr,cm-1):Si-Oa(1016.55cm
-1),W-Ot:969.25cm
-1，W-Oc-W(917.98cm
-1)，W-Oe-W:802.20cm
-1。
Embodiment 2
1. the structure determination of title complex (1)
Choose the monocrystalline RigakuRAXIS-RAPIDX-ray single crystal diffraction instrument mensuration that size is 0.26mm × 0.16mm × 0.21mm, adopt the MoK α radiation (λ=0.071073nm) of graphite monochromator as diffraction light sources, at the temperature of 293 (2) K, with ω-2 θ scan mode, in ° (-18≤h≤19,1.85 °≤θ≤26.14,-20≤k≤26,-27≤l≤26) in scope, collect 7313 point diffractions altogether, wherein 6269 independent point diffractions, crystalline structure is solved by direct method, non-hydrogen atom is obtained by difference Fourier synthesis method, the method determined and revise hydrogen atom is theoretical hydrogenation, isotropy and anisotropy thermal parameter is adopted to carry out complete matrix least-squares refinement to structure respectively to hydrogen atom and non-hydrogen atom, crystalline structure SHELXS-97 direct method, and adopt method of least squares to carry out refine at WINGX Calling SHELXL-97.Some unordered O atoms in title complex carry out refine by using isotropic temperature parameter, and other atom uses anisotropy refine.Wherein, be connected to the unordered O atom on Si atom, being processed respectively and being placed in total occupation rate is on two positions of 1.H atom on C atom carries out hydrogenation according to fourier electron density map.The predominant crystal data of title complex are in table 1.
No. CCDC (No. CCDC is cambridge structure database numbering) of title complex (1): 870624.
The crystallographic data of table 1 title complex title complex (1)
| Molecular formula | Cu 2C 48H 28N 8O 50SiW 12 |
| Molecular weight | 3878.15 |
| Crystallographic system | Othorhombic |
| Spacer | Pbca |
| Length of side a/[nm] | 15.5453(10) |
| Side length b/[nm] | 21.3948(15) |
| Length of side c/[nm] | 22.0731(15) |
| Angle [alpha]/[] | 90 |
| Angle beta/[] | 90 |
| Angle γ/[] | 90 |
| Volume V/[nm 3] | 7341.3(9) |
| Molecules in unit cell | 4 3 --> |
| Density [g m –3] | 3.509 |
| Specific absorbance [mm –1] | 19.409 |
| The consistent factor R of point diffraction 1, WR 2[I＞2σ(I)] | 0.0800, 0.1600 |
| Weighting factor GOF (F 2) | 1.271 |
The infrared spectra of title complex (1) shows typical vibration peak, is respectively Si-Oa (1016.55cm
-1), W-Ot (969.25cm
-1), W-Oc-W (917.98cm is shared at angle
-1), while share W-Oe-W (802.20cm
-1), indicate the existence of α-Keggin-type structure.1110-1702cm is positioned in spectrogram
-1wave number and 3072-3094cm
-1the peak at wave number place is attributed to each interatomic flexible and flexural vibration peak of 1,10-Phenanthroline-5,6-Quinone part.Wide is positioned at 3200-3740cm
-1the stretching vibration peak at place shows the existence of O-H key in water molecules, title complex [Cu (Do)
2(H
2o)]
2(SiW
12o
40) Infrared spectroscopy of (1) is consistent with its crystal structure analysis result.
The crystalline structure of title complex (1) belongs to tetragonal system, Pbca spacer, and main bond distance and bond angle list in table 2, and its crystalline structure as shown in Figure 1.As seen from Figure 1, each complex molecule comprises a Cu
2+ion, two Do parts, a part water and 1/2 (SiW
12o44)
4-ion.Divalent cation Cu
2+with a part water (Cu-OW=2.05 (3)) and the coordination of four nitrogen-atoms (Cu-N1=2.02 (2), Cu-N2=2.08 (2), Cu-N3=1.99 (2), Cu-N4=2.08 (3)).Cu-O and Cu-N bond distance and bond distance's scope thereof are respectively 2.05 and 1.99 ~ 2.08, and this conforms to (table 3.7) with bond distance's scope of other compound mentioned in document.
In title complex (1), coordinated water defines intramolecular O-H with two Sauerstoffatoms coming from silicotungstic acid ... O hydrogen bond (OW-HWB ... O16=2.4 (13), 111 °, OW-HWB ... O15=2.3,104 °, symmetrical code: #1:x+1/2 ,-y-1/2,-z), construct a two-dimentional structure by hydrogen bond action.
The part bond distance of table 2 title complex (1) and bond angle
| Key | Bond distance's [] | Bond angle | Angle [o] |
| Si-O1 | 1.63(4) | Cu-N1 | 2.02(2) |
| Si-O2 | 1.63(4) | Cu-N3 | 1.99(2) |
| Si-O3 | 1.71(4) | Cu-OW | 2.05(3) |
| Si-O4 | 1.64(4) | Cu-N2 | 2.08(2) |
| O1-Si-O2 | 69(2) | Cu-N4 | 2.08(3) |
| O1-Si-O3 | 73.2(19) | N3-Cu-N1 | 175.4(10) |
| O1-Si-O4 | 68(2) | N1-Cu-OW | 89.1(10) |
| O2-Si-O3 | 71(2) | N1-Cu-N2 | 82.1(10) |
| O2-Si-O4 | 68(2) | N3-Cu-N4 | 78.7(9) |
| O3-Si-O4 | 73.8(19) | OW-Cu-N4 | 107.5(11) |
| N3-Cu-OW | 92.2(10) | ||
| N3-Cu-N2 | 99.6(9) | ||
| OW-Cu-N2 | 140.5(11) | ||
| N1-Cu-N4 | 96.7(9) | ||
| N2-Cu-N4 | 111.8(10) |
Conclusion: the invention discloses the synthesis of Cu (II) title complex based on the hybrid inorganic-organic of 1,10-Phenanthroline-5,6-Quinone and silicotungstic acid and the application of photoluminescence.Because metal complex materials has metal center and organic moiety, these two parts all may cause luminescence, the potential using value of these embedded photoluminescent materials in photodiode, solar cell, biological medicine image etc. and being concerned.Test-results shows: Cu (II) title complex of this 1,10-Phenanthroline-5,6-Quinone and silicotungstic acid hydridization can transmitting green light emmission spectrum, has the application prospect that wide in hybrid inorganic-organic embedded photoluminescent material.
Embodiment 3
The concrete instance of organic inorganic hybridization metal complexes in embedded photoluminescent material.
The people such as Liu, by using 1,10-Phenanthroline-5,6-Quinone and α-Keggin-type hydration phospho-wolframic acid for part is by hydrothermal synthesis method, obtain three compounds: (HDo)
6(PW
12o
40)
2(H
2o) (1), [Cu (Do)
2(H
2o)]
2[Cu (Do)
2(PW
12o
40) (H
2o)] (PW
12o
40) (2) and [Pb (Do)
2(PW
12o
40)] (HDo) (3).Study its photoluminescence performance, find that free ligand is at 594nm place display maximum emission wavelength, the emission wavelength of title complex is respectively 592nm, 596nm and 585nm.The part of phase specific ionization, compound (1) blue shift 2nm, compound (2) red shift 2nm, and compound (3) blue shift 9nm.From contrast, the photoluminescence emission maximum spectrum obtaining three compounds is consistent with the maximum emission wavelength of free ligand, and this is owing to the transmitting of 1,10-Phenanthroline-5,6-Quinone part itself.The wavelength blue shift 2nm of compound (1), owing to only containing 1,10-Phenanthroline-5,6-Quinone and α-Keggin-type hydration phospho-wolframic acid in molecule, visible, poly-metal deoxide and the luminescence of polyacid compound on title complex there is no much impacts.Meanwhile, due to compound (2) red shift 2nm, and compound (3) blue shift 9nm, now, the red shift of wavelength and the numerical value of blue shift less, mainly owing to the coordination center of title complex and the difference of metal ion and coordination mode.
Reference:
1.LIUC.B.,WANGQ.Q.,BaiH.Y.,CHEG.B.,ZHANGQ.,LIC.X.,Chin.J.Inorg.Chem.,2014,30(2),391.
Embodiment 4
Based on the application of Cu (II) the title complex green-emitting material of 1,10-Phenanthroline-5,6-Quinone and silicotungstic acid hydridization.
Method: by Perkin-ElmerLS55 spectrophotofluorometer, respectively to the excitation wavelength of this compound (embodiment 1) and the scanning of emission wavelength, selects and determines optimal wavelength.
Conclusion: excitation wavelength and the emission wavelength of this title complex are respectively 365nm and 594nm.
Step: based on 1,10-phenanthroline-5,6-diketone becomes external diameter to be 27mm with Cu (II) the complex monocrystal grinding compressing tablet of silicotungstic acid hydridization, and thickness is the sheet sample of 2-3mm, and the sample pool putting into Perkin-ElmerLS55 fluorescence spectrophotometer is measured.Result: the excitation wavelength lambda of this compound
ex=365nm, λ
em=594nm.
Conclusion:
The invention discloses based on Cu (II) title complex of 1,10-Phenanthroline-5,6-Quinone and silicotungstic acid hydridization and 150 DEG C of high-temperature water process for thermosynthesizing thereof and application.Cu (II) title complex based on 1,10-Phenanthroline-5,6-Quinone and silicotungstic acid hydridization with zero-dimension structural of the present invention is mainly used in embedded photoluminescent material aspect.These two parts all may cause luminescence, the potential using value of these embedded photoluminescent materials in photodiode, solar cell, biological medicine image etc. and being concerned.Test-results shows: Cu (II) title complex of this 1,10-Phenanthroline-5,6-Quinone and silicotungstic acid hydridization can transmitting green light emmission spectrum, has the application prospect that wide in hybrid inorganic-organic embedded photoluminescent material.Should based on the exploitation of the development of Cu (II) title complex of 1,10-Phenanthroline-5,6-Quinone and silicotungstic acid hydridization to optical material or the research to microphysics all has great importance.
Claims (5)
1., based on Cu (II) title complex for the hybrid inorganic-organic of 1,10-Phenanthroline-5,6-Quinone and α-Keggin-type silicotungstic acid, its chemical general formula is [Cu (Do)
2(H
2o)]
2(SiW
12o
40) (1), wherein, Do refers to 1,10-Phenanthroline-5,6-Quinone part.
2. the molecular formula of title complex (1) is [Cu (Do)
2(H
2o)]
2(SiW
12o
40).
3. according to claim 1 based on 1,10-phenanthroline-5, Cu (II) complex monocrystal of the hybrid inorganic-organic of 6-diketone and α-Keggin silicotungstic acid, the related data of crystal is wherein measured by RigakuRAXIS-RAPIDX-ray single crystal diffraction instrument, adopt the MoK α radiation (λ=0.071073nm) of graphite monochromator as diffraction light sources, at the temperature of 293 (2) K, with ω-2 θ scan mode, measure predominant crystal data as follows:
One prepares according to claim 21, 10-phenanthroline-5, the synthetic method of Cu (II) complex monocrystal of the hybrid inorganic-organic of 6-diketone and α-Keggin silicotungstic acid, it is characterized in that: precision takes Gerhardite 0.0241g (0.1mmol), 1, 10-phenanthroline-5, 6-diketone 0.0204g (0.1mmol), and hydration silicotungstic acid 0.2159g (0.075mmol), after 12mL water dissolution, be transferred in the teflon-lined reactor of 20mL, keep three days at 150 DEG C, with 6 DEG C/min of slow coolings, obtain green transparent crystal.
4. Cu (II) title complex of the hybrid inorganic-organic of 1,10-Phenanthroline-5,6-Quinone described in claim 1 and α-Keggin silicotungstic acid is in hybrid inorganic-organic luminescent material, the particularly application of green fluorescence source material aspect.
5. application according to claim 4, wherein said hybrid inorganic-organic luminescent material refers to the hybrid material structurally comprising metal center, organic moiety and inorganic part; Described green fluorescence source material refers to hybrid inorganic-organic luminescent material and measures Solid fluorescene spectrum, the fluorescent material of its Solid fluorescene spectrum wavelength in 492-577nm scope (green light source scope).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622372A (en) * | 2016-12-17 | 2017-05-10 | 聊城大学 | Barium-silicon tungsten oxygen cluster catalyst, preparation method and application thereof |
| CN109637816A (en) * | 2018-12-27 | 2019-04-16 | 东北师范大学 | Cu2S-SiW12/MoS2Combined counter electrode and preparation method thereof and quantum dot sensitized solar battery |
| CN111138460A (en) * | 2020-01-21 | 2020-05-12 | 信阳学院 | Preparation and application of novel complex based on phosphomolybdic acid |
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Non-Patent Citations (3)
| Title |
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| TAPAN KANTI PAINE ET AL.: "Aerobic oxidation of primary alcohols catalyzed by copper complexes of 1,10-phenanthroline-derived ligands", 《DALTON TRANS.》 * |
| 刘春波等: "基于1,10邻菲罗啉5,6二酮和Keggin型多金属氧化物的化合物的水热合成及性质", 《无机化学学报》 * |
| 孟凡霞: "铜-含氮有机配离子-多金属钨酸盐的水热合成、晶体结构及表征", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622372A (en) * | 2016-12-17 | 2017-05-10 | 聊城大学 | Barium-silicon tungsten oxygen cluster catalyst, preparation method and application thereof |
| CN106622372B (en) * | 2016-12-17 | 2018-12-11 | 聊城大学 | A kind of barium silica tungsten oxygen cluster catalyst, preparation method and its usage |
| CN109637816A (en) * | 2018-12-27 | 2019-04-16 | 东北师范大学 | Cu2S-SiW12/MoS2Combined counter electrode and preparation method thereof and quantum dot sensitized solar battery |
| CN111138460A (en) * | 2020-01-21 | 2020-05-12 | 信阳学院 | Preparation and application of novel complex based on phosphomolybdic acid |
| CN111138460B (en) * | 2020-01-21 | 2023-01-31 | 信阳学院 | Preparation and application of novel complex based on phosphomolybdic acid |
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