CN104558055B - There is oxygen ether pair triazole nitric acid nickel complex of potential fluorescent material and preparation method thereof - Google Patents
There is oxygen ether pair triazole nitric acid nickel complex of potential fluorescent material and preparation method thereof Download PDFInfo
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- CN104558055B CN104558055B CN201510088211.XA CN201510088211A CN104558055B CN 104558055 B CN104558055 B CN 104558055B CN 201510088211 A CN201510088211 A CN 201510088211A CN 104558055 B CN104558055 B CN 104558055B
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- triazole
- triazoles
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- oxygen ether
- nitric acid
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000001301 oxygen Substances 0.000 title claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title claims abstract description 7
- 150000003852 triazoles Chemical class 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 7
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 title abstract description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 18
- -1 triazole nickel nitrate Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 7
- 239000000706 filtrate Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000012046 mixed solvent Substances 0.000 abstract description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- JTYRXXKXOULVAP-UHFFFAOYSA-N 1,2-dibromo-3-phenoxybenzene Chemical compound BrC1=CC=CC(OC=2C=CC=CC=2)=C1Br JTYRXXKXOULVAP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses double triazole nitric acid the nickel complex { [Ni (L) of oxygen ether2(NO3)2]·CHCl3(1) structural motif as shown in Figure 1.{ [Ni (L) is also disclosed simultaneously2(NO3)2]·CHCl3} (1).The preparation method of (L=1 (4 (4 (1,2,4 triazoles of 1H, 1 base) phenoxy group) phenyl) 1,2,4 triazoles of 1H).It is using " room temperature volatility process ", i.e. L and Ni (NO3)2·6H2O is in CHCl3、CH3Filter after stirring half an hour in the mixed solvent of OH and water, filtrate room temperature obtains the light green color rhabdolith for being suitable for X ray single crystal diffractions after volatilizing two weeks.The present invention further discloses the double triazole nitric acid nickel complex of oxygen ether as potential fluorescent material in terms of application.
Description
The present invention obtains state natural sciences fund general project (21471113), young top-notch personnel's support plan, day
Education Commission of Jinshi City general project (20140506), Tianjin Normal University's Middl-age and youth faculty Academic innovations propulsion planning item
(52XC1401), Tianjin Municipal Commission of Science and Technology general project (11JCYBJC03600) and Tianjin innovation team of institution of higher education culture meter
Draw the subsidy of (TD12-5038).
Technical field
The invention belongs to organic and Inorganic synthese technical field, is related to double triazole nitric acid the nickel complex { [Ni (L) of oxygen ether2
(NO3)2]·CHCl3(1) (L=1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4-
Triazole) preparation method and the application as potential fluorescent material.
Background technology
1,2,4- triazole and its derivant have the coordination feature of pyrazoles and imidazoles concurrently, are that the stronger bridging of coordination ability is matched somebody with somebody
Body, has synthesized at present and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound.These parts can be former with the nitrogen on 1,2
Son and metallic ion coordination formation N1, N2- bridging patterns, for 4 unsubstituted 1,2,4- triazole derivatives can pass through 2,4
On nitrogen-atoms formed N2, N4- bridging patterns, this N2, N1 of the N4- bridgings pattern with imidazoles in metalloenzyme, N3- bridging patterns
Similar.For the specific use of triazole class compounds is also manifested by the design of molecular device, synthesis has different dimensions
Metal complex is to complete the vital step of device.
The present invention is employing " room temperature volatility process ", i.e. L and Ni (NO3)2·6H2O is in CHCl3、CH3The mixing of OH and water is molten
Filter after stirring half an hour in agent, filtrate room temperature volatilizees and obtains within two weeks the light green color rhabdolith for being suitable for X-ray single crystal diffraction
{[Ni(L)2(NO3)2]·CHCl3(1) (L=1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -
1H-1,2,4- triazoles).The coordination compound is applied in terms of being alternatively arranged as potential fluorescent material.
Content of the invention
Further object is that providing a kind of oxygen ether double triazole nitric acid nickel complex { [Ni (L)2(NO3)2]·
CHCl3(1) (L=1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) list
Crystalline substance and preparation method thereof.
For this current inventor provides following technical scheme：
Double triazole nitric acid the nickel complex { [Ni (L) of oxygen ether2(NO3)2]·CHCl3} (1) (L = 1-(4-(4-(1H-1,
2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) structural motif as shown in Figure 1.
The present invention further discloses double triazole nitric acid the nickel complex { [Ni (L) of oxygen ether2(NO3)2]·CHCl3} (1) (L
=1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) monocrystalline, it is characterised in that
The mono-crystalline structures adopt APEX II CCD single crystal diffractometers, using through graphite monochromatised Mok alpha rays (λ=0.71073
) it is incident radiation, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, from difference
Value Fourier electron density map solves single crystal data using SHELXL-97 direct methods：
The crystallographic data of 1. coordination compound 1 of table
Double triazole nitric acid the nickel complex { [Ni (L) of oxygen ether of the present invention2(NO3)2]·CHCl3} (1) (L = 1-(4-
(4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) monocrystalline preparation method, its feature exists
Using " room temperature volatility process ", i.e. L and Ni (NO3)2·6H2O is in CHCl3、CH3Mistake after stirring half an hour in the mixed solvent of OH and water
Filter, filtrate room temperature volatilize two weeks after preparing the coordination compound
L.
A preferred example of the invention：
The preparation of 1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles (L)
" one kettle way " is adopted in polar solvent, by 4,4 '-dibromodiphenyl ether, 1H-1,2,4- triazoles, potassium carbonate and copper oxide
Prepare in a heated condition；The bromo- 4- of wherein 1- (4- bromobenzene epoxides) benzene：1H-1,2,4- triazoles：Potassium carbonate：Copper oxide mole
Than for 2:10:30:1；
4,4 '-dibromodiphenyl ether 1H-1,2,4- triazoles
Preferably 4,4 '-dibromodiphenyl ether of the invention：1H-1,2,4- triazoles：Potassium carbonate：The mol ratio of copper oxide is 2:10:
30:1；Reaction temperature 80-200 DEG C, response time 12-120 hour.In polar solvent, adopt " one kettle way ", by 4,4 '-two
Dibromodiphenyl ether, 1H-1,2,4- triazoles, potassium carbonate and copper oxide prepare the organic compound in a heated condition；
Presently preferred embodiment
1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles (L) (0.1
) and Ni (NO mmol3)2·6H2O (0.2 mmol) is in CHCl3(10 mL)、CH3OH (8 mL) and H2The mixing of O (1 mL)
Filter after stirring half an hour in solvent, filtrate room temperature obtains the light green color bulk crystals of X-ray single crystal diffraction after volatilizing two weeks.
Yield：40%.Elementary analysiss (C33H25Cl3N14NiO8) theoretical value (%)：C, 43.52；H, 2.77；N, 21.53.Measured value：C,
43.58；H, 2.82；N, 21.49.
The present invention further discloses double triazole nitric acid the nickel complex { [Ni (L) of oxygen ether2(NO3)2]·CHCl3} (1) (L
=1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) can be used as potential fluorescence
Applied in terms of material.
A kind of double triazole nitric acid the nickel complex { [Ni (L) of oxygen ether disclosed by the invention2(NO3)2]·CHCl3} (1) (L =
1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) monocrystalline had the advantage that and
Feature is：
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) { [Ni (L) prepared by the present invention2(NO3)2]·CHCl3} (1) (L = 1-(4-(4-(1H-1,2,4-
Triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) low production cost, method simplicity, suitable large-scale production.
Description of the drawings
Fig. 1：The crystal structure primitive figure of coordination compound 1；
Fig. 2：The one-dimensional catenary structure figure of coordination compound 1.
Specific embodiment
With reference to embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it
The scope of the present invention is limited by any way.Raw materials used 4,4 '-dibromodiphenyl ether, 1H-1,2,4- triazoles, potassium carbonate and oxygen
Change copper etc. to be commercially available.All raw materials are bought from chemical reagents corporation both domestic and external, not through continuation purification
Directly use.
Embodiment 1
4,4 '-dibromodiphenyl ether：1H-1,2,4- triazoles：Potassium carbonate：The mol ratio of copper oxide is 2:10:30:1
CuO (0.5 is separately added in the 50 mL three neck round bottom flask equipped with magneton, reflux condenser and thermometer
Mmol), potassium carbonate (15 mmol), 1H-1,2,4- triazoles (5 mmol), 4,4 '-dibromodiphenyl ether (1 mmol) and 20
mL DMF.Stirring is started 100oC, reacts 24 hours.After reaction terminates, reactant liquor is down to room temperature, is filtered, filtrate adds
100 mL water, separate out a large amount of precipitations, and sucking filtration collects filter cake, 1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) benzene
Base) -1H-1,2,4- triazoles (L).Yield 60%.
Embodiment 2
1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles (L) (0.1
) and Ni (NO mmol3)2·6H2O (0.2 mmol) is in CHCl3(10 mL)、CH3OH (8 mL) and H2The mixing of O (1 mL)
Filter after stirring half an hour in solvent, filtrate room temperature obtains the light green color bulk crystals of X-ray single crystal diffraction after volatilizing two weeks.
Yield：40%.Elementary analysiss (C33H25Cl3N14NiO8) theoretical value (%)：C, 43.52；H, 2.77；N, 21.53.Measured value：C,
43.58；H, 2.82；N, 21.49.
Embodiment 3
Crystal structure determination adopts APEX II CCD single crystal diffractometers, using through graphite monochromatised Mok alpha ray (λ
=0.71073) be incident radiation, withω-2θScan mode collects point diffraction, obtains structure cell through least square refinement
Parameter, solves crystal structure from difference Fourier electron density map using software, and through Lorentz lorentz and polarity effect correction.All
H atom synthesized and determined through preferable position calculation by difference Fourier.Detailed axonometry data are shown in Table 1.Structural motif
See that Fig. 1, one-dimensional catenary structure are shown in Fig. 2.
The crystallographic data of 1. coordination compound 1 of table
Embodiment 4
The concrete instance that dyestuff or luminous agent are used
Method：Differentiated pulse volt-ampere (DPV) the curve negotiating Princeton Applied Research Laboratory of dye solution is developed
2273 electrochemical workstations of PARSTAT are measured.The DPV tests of solution adopt three-electrode system, and glass-carbon electrode is working electrode,
Auxiliary electrode is platinum plate electrode, homemade Ag/AgNO3Electrode is reference electrode；Acetonitrile of the electrolyte for 0.1mol L-1TBAP
Solution.Reversible point is reduced to as internal standard, obtaining the corrected value between test system and standard hydrogen electrode system with Oxidation of Ferrocene.
Monochromatic incident illumination photoelectric transformation efficiency (IPCE) describes photoelectric transformation efficiencies of the DSCs under monochromatic light action, is to turn
Move on to the electron number of external circuit and the ratio of incident illumination subnumber.During measurement, use 500 W xenon lamps as light source, incident illumination is passed through
The multifunctional assembled grating spectrograph of WDS-5 types obtains the monochromatic light under different wave length λ；Monochromatic light exposure is in the light sun of battery
Pole, reads current value I by Keithley2400 digital sourcemeters.Monochromatic good fortune illumination is micro- by USB4000 plug-and-play
Type light spectral instrument is measured.
Step：In order to have any actual knowledge of dyestuff in TiO2Adsorbance on film, by dye sensitization TiO2Nanometer crystal film (geometric surface
Product is about 1 cm2) it is immersed in 10 mL, 0.01 mol L-1Sodium hydroxide methanol solution in overnight, treat that dyestuff is desorbed completely
The absorbance of solution is determined afterwards.Washed one's face and rinsed one's mouth according to absorbance and molar absorptivity and can calculate dyestuff on unit area nanometer crystal film
Adsorbance.The adsorbance of the coordination compound is 6.3 × 10-4mol/cm2.
As a result：Compared with the methanol solution of dyestuff, dyestuff is in TiO2Absorption spectrum on film substantially broadens and red shift.This
Show dye molecule in TiO2Define the J- aggregations of first and tail.Say from the operation principle of DSCs, the light that dye aggregation causes
Spectrum width and red shift are highly beneficial for widening for the photoelectric respone scope of dyestuff.But at the same time, dye aggregation is known from experience
Its electron injection efficiency is substantially reduced, so as to cause the degraded performance of DSCs.So, generally add in dye solution co-adsorption
Agent is suppressing the aggregation of dyestuff.The coordination compound is in methanol solution and its in TiO2The fluorometric investigation of the purple solution on membrane electrode is adopted
With 2.5 × 10-5The methanol solution of mol/L, maximum emission wavelength are located at 588 nm.
After the preferred embodiment for describing in detail, it is familiar with the skilled worker and is clearly understood that, without departing from above-mentioned
Various change and modification can be carried out under claim and spirit, all technical spirits according to the present invention are to above example institute
Any simple modification, equivalent variations and the modification that makees, belongs to the scope of technical solution of the present invention.And the present invention is not also illustrated
The restriction of example embodiment in book.
Claims (1)
1. the application in terms of the double triazole nickel nitrate complex monocrystals of oxygen ether are as potential fluorescent material, it is characterised in that the monocrystalline
Structure adopts APEX II CCD single crystal diffractometers, and using through graphite monochromatised Mok alpha rays, λ=0.71073 is incidence
Radiation, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, from difference Fourier
Electron density map solves single crystal data using software：
The structural formula of the wherein double triazole nickel nitrate complex monocrystals of oxygen ether is { [Ni (L)2(NO3)2]·CHCl3, L=1- (4-
(4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles.
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