CN104610313A - Oxy-ether-bis(triazole) cadmium complex with potential fluorescent materials and preparation method thereof - Google Patents

Oxy-ether-bis(triazole) cadmium complex with potential fluorescent materials and preparation method thereof Download PDF

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CN104610313A
CN104610313A CN201510088001.0A CN201510088001A CN104610313A CN 104610313 A CN104610313 A CN 104610313A CN 201510088001 A CN201510088001 A CN 201510088001A CN 104610313 A CN104610313 A CN 104610313A
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triazole
dmf
phenyl
cadmium complex
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CN104610313B (en
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王英
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Tianjin Normal University
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    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/08Cadmium compounds
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/188Metal complexes of other metals not provided for in one of the previous groups

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Abstract

The invention discloses an oxy-ether-bis(triazole) cadmium complex {[Cd(L)2(NO3)2].DMF} (1). A structural motif of the oxy-ether-bis(triazole) cadmium complex is shown in a drawing 1 in the specification. Meanwhile, the invention also discloses a preparation method of {[Cd(L)2(NO3)2].DMF} (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl)phenoxyl)phenyl)-1H-1,2,4-triazole, DMF=N,N'-dimethyl formamide). A yellow bulk crystal suitable for X-ray single crystal diffraction is obtained by adopting a solvothermal method which comprises the steps that Cd(NO3)2.6H2O, L, DMF and H2O react for three days at 90 DEG C and then a reaction liquid is slowly cooled to the room temperature. The invention further discloses application of the oxy-ether-bis(triazole) cadmium complex {[Cd(L)2(NO3)2].DMF} (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl)phenoxyl)phenyl)-1H-1,2,4-triazole) as a potential fluorescent material.

Description

Two triazole cadmium complex of oxygen ether with potential fluorescent material and preparation method thereof
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to and state two triazole the cadmium complex { [Cd (L) of oxygen ether 2(NO 3) 2] DMF} ( 1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) 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 " solvent-thermal method ", i.e. Cd (NO 3) 26H 2o, L, DMF and H 2o is 90 ounder C, yellow the bulk crystals { [Cd (L) that room temperature obtains applicable X-ray single crystal diffraction is slowly down in reaction for three days afterwards 2(NO 3) 2] DMF} ( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole).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 oxygen ether two triazole cadmium complex { [Cd (L) 2(NO 3) 2] DMF} ( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole the cadmium complex { [Cd (L) of oxygen ether 2(NO 3) 2] DMF} ( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) structural motif as shown in Figure 1.
The present invention further discloses two triazole the cadmium complex { [Cd (L) of oxygen ether 2(NO 3) 2] DMF} ( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) 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
Two triazole the cadmium complex { [Cd (L) of oxygen ether of the present invention 2(NO 3) 2] DMF} ( 1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline, its feature is at employing " solvent-thermal method ", i.e. Cd (NO 3) 26H 2o, L, DMF and H 2o is 90 ounder C, reaction is slowly down to room temperature for three days afterwards to prepare this title complex
L
The present invention's preferred example:
The preparation of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L)
Adopt " one kettle way " at polar solvent, by 4,4 '-dibromodiphenyl ether, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are prepared in a heated condition; The wherein bromo-4-of 1-(4-bromine phenoxy group) benzene: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1;
4,4 '-dibromodiphenyl ether 1H-1,2,4-triazole
The present invention preferably 4,4 '-dibromodiphenyl ether: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour.In polar solvent, adopt " one kettle way ", by 4,4 '-dibromodiphenyl ether, 1H-1, this organic compound prepared in a heated condition by 2,4-triazole, salt of wormwood and cupric oxide;
Another preferred embodiment of the present invention
1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L) (0.1 mmol), Cd (NO 3) 26H 2o (0.2 mmo), DMF (6 mL) and H 2o (2 mL), is put in 23 mL water heating kettles.90 oc heats and is slowly down to room temperature afterwards in three days, obtains the yellow bulk crystals of applicable X-ray single crystal diffraction after driving still.Productive rate: 20%.Ultimate analysis (C 35h 31cdN 15o 9) theoretical value (%): C, 45.79; H, 3.40; N, 22.88.Measured value: C, 45.80; H, 3.42; N, 22.89.
The present invention further discloses two triazole the cadmium complex { [Cd (L) of oxygen ether 2(NO 3) 2] DMF} ( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) can be used as potential fluorescent material aspect and applied.
Two triazole the cadmium complex { [Cd (L) of a kind of oxygen ether disclosed by the invention 2(NO 3) 2] DMF} ( 1) advantage and disadvantage that has of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) 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) { [Cd (L) prepared by the present invention 2(NO 3) 2] DMF} ( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) 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 1one-dimensional catenary 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 4,4 '-dibromodiphenyl ether, 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
4,4 '-dibromodiphenyl ether: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1
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), 4,4 '-dibromodiphenyl ether (1 mmol) and 20 mL DMF.Start and be stirred in 100 oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, filter, filtrate adds 100 mL water, separate out a large amount of precipitation, suction filtration, collect filter cake 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L).Yield 60%.
Embodiment 2
1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L) (0.1 mmol), Cd (NO 3) 26H 2o (0.2 mmo), DMF (6 mL) and H 2o (2 mL), is put in 23 mL water heating kettles.90 oc heats and is slowly down to room temperature afterwards in three days, obtains the yellow bulk crystals of applicable X-ray single crystal diffraction after driving still.Productive rate: 20%.Ultimate analysis (C 35h 31cdN 15o 9) theoretical value (%): C, 45.79; H, 3.40; N, 22.88.Measured value: C, 45.80; H, 3.42; N, 22.89.
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 one-dimensional catenary 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 5.5 × 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 584 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. two triazole the cadmium complex { [Cd (L) of oxygen ether 2(NO 3) 2] DMF} ( 1) structural motif as shown in Figure 1:
L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole.
2. the monocrystalline of the two triazole cadmium complex of oxygen ether described in claim 1, 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. two triazole the cadmium complex { [Cd (L) of oxygen ether described in claim 1 2(NO 3) 2] DMF} ( 1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole), it is characterized in that it adopts " solvent-thermal method ", i.e. Cd (NO 3) 26H 2o, L, DMF and H 2o is 90 ounder C, reaction is slowly down to room temperature for three days afterwards to prepare this title complex
L。
4. two triazole the cadmium complex { [Cd (L) of oxygen ether described in claim 1 2(NO 3) 2] DMF} ( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) as the application of potential fluorescent material aspect.
CN201510088001.0A 2015-02-26 2015-02-26 Two triazole cadmium complex of oxygen ether with potential fluorescent material and preparation method thereof Expired - Fee Related CN104610313B (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN105524119A (en) * 2016-01-05 2016-04-27 天津师范大学 1, 4-dimethyl-2, 5-dimethylene bistriazole ferrous complex single crystal and application thereof
CN105524003A (en) * 2016-01-05 2016-04-27 天津师范大学 4-(4-(4-(4H-1,2,4-triazol-4-yl) phenoxy) phenyl)-4H-1,2,4-triazol-single crystal and application thereof
CN111471038A (en) * 2020-03-12 2020-07-31 广西师范大学 Tetragonal system Cd-MOF crystal material and synthesis method and application thereof

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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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524119A (en) * 2016-01-05 2016-04-27 天津师范大学 1, 4-dimethyl-2, 5-dimethylene bistriazole ferrous complex single crystal and application thereof
CN105524003A (en) * 2016-01-05 2016-04-27 天津师范大学 4-(4-(4-(4H-1,2,4-triazol-4-yl) phenoxy) phenyl)-4H-1,2,4-triazol-single crystal and application thereof
CN111471038A (en) * 2020-03-12 2020-07-31 广西师范大学 Tetragonal system Cd-MOF crystal material and synthesis method and application thereof
CN111471038B (en) * 2020-03-12 2022-09-30 广西师范大学 Tetragonal system Cd-MOF crystal material and synthesis method and application thereof

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