CN104610380A - Potential fluorescent material containing tri-iodo-aniline-3,3-azole terephthalic cobalt complex and preparation method thereof - Google Patents

Potential fluorescent material containing tri-iodo-aniline-3,3-azole terephthalic cobalt complex and preparation method thereof Download PDF

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CN104610380A
CN104610380A CN201510088006.3A CN201510088006A CN104610380A CN 104610380 A CN104610380 A CN 104610380A CN 201510088006 A CN201510088006 A CN 201510088006A CN 104610380 A CN104610380 A CN 104610380A
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tpa
triazole
amine
terephthalic acid
phenyl
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CN104610380B (en
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王英
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Tianjin Normal University
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    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06Cobalt compounds
    • C07F15/065Cobalt compounds without a metal-carbon linkage
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06Cobalt compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18Metal complexes
    • C09K2211/187Metal complexes of the iron group metals, i.e. Fe, Co or Ni

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Abstract

The invention discloses a potential fluorescent material containing tri-iodo-aniline-3,3-azole terephthalic cobalt complex {[Cd (L) (tpa)].DMF.3H2O}((b)1 (/b)), and the structural motif thereof is shown in FIG 1. The invention also discloses a preparation method of the {[Cd (L) (tpa)].DMF.3H2O}((b)1 (/b)), (L = tri(4-triazole phenyl) amine), DMF = N, N'- dimethyl formamide, tpa = terephthalic acid). The preparation method is implemented by using a 'normal temperature volatilization method', i.e. after L, tpa and Cd (Ac) 2.4H2O are stirred for half an hour in a mixed solvent of CH3OH, H2O and DMF, the obtained object is filtered, and filtrate is volatilized in two weeks at normal temperature, so that yellow rod crystals suitable for X-ray single crystal diffraction are obtained. The invention further discloses an application of the tri-iodo-aniline-3,3-azole terephthalic cobalt complex as a potential fluorescent material.

Description

Phenyl triiodide amine three triazole terephthalic acid cobalt complex with potential fluorescent material and preparation method thereof
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H 2o} ( 1) preparation method of (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) and the application as potential fluorescent material.
Background technology
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention adopts " normal temperature volatilization method ", i.e. tpa, L, Co (Ac) 24H 2o is at CH 3oH, H 2filter after stirring half an hour in the mixed solvent of O and DMF, filtrate normal temperature obtains pink colour rhabdolith { [Co (L) (tpa)] DMF3H of applicable X-ray single crystal diffraction after volatilizing two weeks 2o} ( 1) (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid).This title complex also can be used as potential fluorescent material aspect and is applied.
Summary of the invention
Another object of the present invention is to provide a kind of phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H 2o} ( 1) (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H 2o} ( 1) (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) structural motif as shown in Figure 1.
The present invention further discloses phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H 2o} ( 1) (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) monocrystalline, it is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize SHELXL-97 direct method to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex 1crystallographic data
Phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H of the present invention 2o} ( 1) preparation method of (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) monocrystalline, its feature is at employing " normal temperature volatilization method ", i.e. tpa, L, Co (Ac) 24H 2o is at CH 3oH, H 2filter after stirring half an hour in the mixed solvent of O and DMF, filtrate normal temperature volatilizees two weeks to prepare this title complex
L tpa。
The present invention's preferred example:
Three (4-triazole phenyl) amine) preparation of (L)
Adopt " one kettle way " at polar solvent, three (4-phenyl-iodide) amine, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are prepared in a heated condition; Wherein three (4-phenyl-iodide) amine: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:15:30:1;
three (4-phenyl-iodide) amine 1H-1,2,4-triazole
The present invention is three (4-phenyl-iodide) amine: 1H-1,2,4-triazole preferably: salt of wormwood: the mol ratio of cupric oxide is 2:15:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour.In polar solvent, adopt " one kettle way ", three (4-phenyl-iodide) amine, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are prepared this organic compound in a heated condition;
Another preferred embodiment of the present invention
Tpa (0.1 mmol), Co (Ac) 24H 2o (0.2 mmol) and three (4-triazole phenyl) amine) (L) (0.1 mmol) be at CH 3oH (4 mL), H 2filter after stirring half an hour in the mixed solvent of O (2 mL) and DMF (10 mL), filtrate normal temperature obtains the pink colour rhabdolith of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 20%.Ultimate analysis (C 35h 35coN 11o 8) theoretical value (%): C, 52.77; H, 4.43; N, 19.34.Measured value: C, 52.69; H, 4.48; N, 19.38.
The present invention further discloses phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H 2o} ( 1) (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) can be used as potential fluorescent material aspect and applied.
A kind of phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H disclosed by the invention 2o} ( 1) advantage and disadvantage that has of (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) monocrystalline is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) { [Co (L) (the tpa)] DMF3H prepared by the present invention 2o} ( 1) (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) production cost is low, method is easy, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1: title complex 1crystalline structure primitive figure;
Fig. 2: title complex 1two-dimensional layered structure figure.
Embodiment
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, never means that it limits the scope of the invention by any way.Raw materials used three (4-phenyl-iodide) amine, 1H-1,2,4-triazole, salt of wormwood and cupric oxide etc. all have commercially available.All raw materials are all buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.
Embodiment 1
Three (4-phenyl-iodide) amine: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:15:30:1
CuO (0.5 mmol), salt of wormwood (15 mmol), 1H-1 is added respectively in 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 2,4-triazole (5 mmol), three (4-phenyl-iodide) amine (1 mmol) and 20 mL DMF.Start and be stirred in 150 oc, reacts 60 hours.After reaction terminates, reaction solution is down to room temperature, filter, filtrate adds 100 mL water, separates out and precipitates in a large number, suction filtration, collects filter cake, three (4-triazole phenyl) amine (L).Yield 78.3%.
Embodiment 2
Tpa (0.1 mmol), Co (Ac) 24H 2o (0.2 mmol) and three (4-triazole phenyl) amine) (L) (0.1 mmol) be at CH 3oH (4 mL), H 2filter after stirring half an hour in the mixed solvent of O (2 mL) and DMF (10 mL), filtrate normal temperature obtains the pink colour rhabdolith of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 20%.Ultimate analysis (C 35h 35coN 11o 8) theoretical value (%): C, 52.77; H, 4.43; N, 19.34.Measured value: C, 52.69; H, 4.48; N, 19.38.
Embodiment 3
Crystal structure determination adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz lorentz and polarizing effect correction.All H atom are synthesized by difference Fourier and are determined through desirable position calculation.Detailed axonometry data are in table 1.Structural motif is shown in Fig. 1, and two-dimensional layered structure is shown in Fig. 2.
Table 1. title complex 1crystallographic data
Embodiment 4
The concrete instance that dyestuff or luminous agent use
Method: PARSTAT 2273 electrochemical workstation of differentiated pulse volt-ampere (DPV) the curve negotiating Princeton Applied Research Laboratory development of dye solution is measured.The DPV test of solution adopts three-electrode system, and glass-carbon electrode is working electrode, and supporting electrode is platinum plate electrode, homemade Ag/AgNO 3electrode is reference electrode; Electrolytic solution is the acetonitrile solution of 0.1molL-1TBAP.Reduce reversible point to for interior mark with Oxidation of Ferrocene, obtains the correction value between test system and standard hydrogen electrode system.
Monochromatic incident light photoelectric transformation efficiency (IPCE) describes the photoelectric transformation efficiency of DSCs under monochromatic ray effect, is transfer to the electronic number of external circuit and the ratio of incident light subnumber.During measurement, use 500 W xenon lamps as light source, the monochromatic ray of incident light under the multifunctional assembled grating spectrograph of WDS-5 type obtains different wave length λ; Monochromatic light exposure, in the light anode of battery, reads current value I by Keithley2400 digital sourcemeter.Monochromatic good fortune illumination is measured by USB4000 plug-and-play Miniature optical linear light spectrometer.
Step: in order to definitely understand dyestuff at TiO 2adsorptive capacity on film, by dye sensitization TiO 2(geometric area is about 1 cm to nanometer crystal film 2) be immersed in 10 mL 0.01 molL -1sodium hydroxide methanol solution in spend the night, treat that the absorbancy of attached mensuration solution separated completely by dyestuff.Wash one's face and rinse one's mouth according to absorbancy and molar absorptivity and can calculate the adsorptive capacity of dyestuff on unit surface nanometer crystal film.The adsorptive capacity of this title complex is 5.9 × 10 -4mol/cm 2.
Result: compared with the methanol solution of dyestuff, dyestuff is at TiO 2absorption spectrum on film all obviously broadens and red shift.This shows that dye molecule is at TiO 2define the J-aggregate of first also tail.From the principle of work of DSCs, the spectrum broadening that dye aggregation causes and red shift are very favourable for the widening of photoelectric response scope of dyestuff.But meanwhile, dye aggregation cognition reduces its electron injection efficiency greatly, thus causes the degraded performance of DSCs.So, in dye solution, usually add coadsorbent to suppress the gathering of dyestuff.This title complex is in methanol solution and at TiO 2the fluorometric investigation of the purple solution on membrane electrode adopts 2.5 × 10 -5the methanol solution of mol/L, maximum emission wavelength is positioned at 578 nm.
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.And the present invention is not also by the restriction of example embodiment in specification sheets.

Claims (4)

1. phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H 2o} ( 1) structural motif as shown in Figure 1:
L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid.
2. the monocrystalline of phenyl triiodide amine three triazole terephthalic acid cobalt complex described in claim 1, it is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex 1crystallographic data
3. phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H described in claim 1 2o} ( 1) preparation method of (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid), it is characterized in that it adopts " normal temperature volatilization method ", i.e. tpa, L, Co (Ac) 24H 2o is at CH 3oH, H 2filter after stirring half an hour in the mixed solvent of O and DMF, filtrate normal temperature volatilizees two weeks to prepare this title complex
L tpa。
4. phenyl triiodide amine three triazole terephthalic acid cobalt complex { [Co (L) (tpa)] DMF3H described in claim 1 2o} ( 1) (L=tri-(4-triazole phenyl) amine, DMF=N, N'-dimethyl formamide, tpa=terephthalic acid) as the application of potential fluorescent material aspect.
CN201510088006.3A 2015-02-26 2015-02-26 Triazole terephthalic acid (TPA) cobalt complex of phenyl triiodide amine three with potential fluorescent material and preparation method thereof Expired - Fee Related CN104610380B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524123A (en) * 2016-01-05 2016-04-27 天津师范大学 1, 4-dimethyl-2, 5-dimethylene bistriazole nickel complex single crystal and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276658A (en) * 2011-06-13 2011-12-14 天津师范大学 Mixed ligand cobalt (II) coordination compound as well as preparation method and application thereof
CN104193691A (en) * 2014-09-11 2014-12-10 南京农业大学 Synthesis methods of tri-(4-triazolyl phenyl) amine and tri-(4-triazolyl phenyl)amine cadmium complex

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524123A (en) * 2016-01-05 2016-04-27 天津师范大学 1, 4-dimethyl-2, 5-dimethylene bistriazole nickel complex single crystal and application thereof

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