CN105541873A - Triazine copper propionate complex single crystal and preparation method and application thereof - Google Patents

Triazine copper propionate complex single crystal and preparation method and application thereof Download PDF

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CN105541873A
CN105541873A CN201610001402.2A CN201610001402A CN105541873A CN 105541873 A CN105541873 A CN 105541873A CN 201610001402 A CN201610001402 A CN 201610001402A CN 105541873 A CN105541873 A CN 105541873A
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triazine
propionic acid
single crystal
copper complex
preparation
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王中良
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Tianjin University
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
    • C07F1/00Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • 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
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13Crystalline forms, e.g. polymorphs
    • CCHEMISTRY; METALLURGY
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18Metal complexes
    • C09K2211/188Metal complexes of other metals not provided for in one of the previous groups

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Abstract

The invention discloses a triazine copper propionate complex single crystal. The structure of the triazine copper propionate complex single crystal is [CuL(H2O)].1.5H2O, wherein L=1, 3, 5-triazine-2, 4, 6- tri-aminopropionic acid. The invention further discloses a preparation method of the single crystal. According to the preparation method, a normal temperature volatilization method is adopted, L and Cu(Ac)2.H2O are stirred in water for half an hour, and then filtration is conducted, and after filtrate volatilizes for two weeks at the normal temperature, the blue block-state crystal suitable for X-ray single crystal diffraction is obtained, wherein the mole ratio of L to Cu(Ac)2.H2O is 1: 1. The invention further discloses application of the triazine copper propionate complex single crystal to detection of adsorbing capacity of dye or a light-emitting agent with the triazine copper propionate complex single crystal as a fluorescent material.

Description

Triazine propionic acid copper complex monocrystalline and preparation method thereof and application
The present invention obtains the subsidy that state natural sciences fund general project (21471113), Tianjin Education Commission general project (20140506) and Tianjin Normal University's Middl-age and youth faculty Academic innovations advance planning item (52XC1401).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to triazine propionic acid copper complex monocrystalline [CuL (H 2o)] 1.5H 2the preparation method of O and the application as potential fluorescent material, wherein, L=1,3,5-triazine-2,4,6-triamino propionic acid.
Background technology
Coordination chemistry is inorganic chemical important branch, is many multi-disciplinary point of crossing, defines many brand-new frontier branches of science be full of vitality.Wherein, carboxylic-acid part, due to a large amount of existence of the weak interaction such as special and hydrogen bond of its coordination ability, makes its research development in recent years rapid.In the research of supramolecular chemistry, receive the concern of domestic and international chemist, in molecular recognition, catalysis, absorption etc., have goodish application.
The present invention adopts normal temperature volatilization method, i.e. L and Cu (Ac) 2h 2o filters stir half an hour in water after, and filtrate normal temperature obtains applicable X-ray single crystal diffraction blue bulk crystal structure after volatilizing two weeks is [CuL (H 2o)] 1.5H 2o, wherein, L=1,3,5-triazine-2,4,6-triamino propionic acid.This title complex also can be used as potential fluorescent material aspect and is applied.
Summary of the invention
Current inventor provides following technical scheme for this reason:
Its structure is as follows:
[CuL (H 2o)] 1.5H 2o, wherein
L=1,3,5-triazine-2,4,6-triamino propionic acid.
The present invention further discloses the preparation method of triazine propionic acid copper complex monocrystalline, it is characterized in that it adopts normal temperature volatilization method, by L and Cu (Ac) 2h 2o filters stir half an hour in water after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:Cu (Ac) 2h 2the mol ratio of O is 1:1;
The structure of triazine propionic acid copper complex monocrystalline is [CuL (H 2o)] 1.5H 2o; Wherein L=1,3,5-triazine-2,4,6-triamino propionic acid;
L。
The present invention further discloses triazine propionic acid copper complex monocrystalline as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent
Experimental result shows:
(1) complex monocrystal in embodiment 2 has good selectivity and susceptibility to dyestuff, and detectability reaches 0.1ppm.
(2) can detect the luminous agent of trace, detection limit reaches 5.0 μ g/L.
(3) complex monocrystal that prepared by embodiment 2 is 1.4 × 10 for the adsorptive capacity of dyestuff -3mol/cm 2.
The present invention's preferred example:
The preparation of 1,3,5-triazines-2,4,6-triamino propionic acid (L)
1,3,5-triazines-2,4,6-triamine: the mol ratio of 3-bromo-propionic acid is 1:4
In 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add 1,3,5-triazines-2,4,6-triamine (1mmol) and 3-bromo-propionic acid (4mmol) respectively, start and be stirred in 150 oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, the precipitation obtained is added 100mL hot methanol, after stirring and dissolving, filter, filtrate is slowly volatilized and is obtained white solid, yield 85%;
1,3,5-triazines-2,4,6-triamine 3-bromo-propionic acid.
The mol ratio of the present invention's preferred 1,3,5-triazines-2,4,6-triamine and 3-bromo-propionic acid is 1:4; Temperature of reaction 150 DEG C, 24 hours reaction times.Adopt " one kettle way ", 1,3,5-triazines-2,4,6-triamine and 3-bromo-propionic acid are prepared 1,3,5-triazines-2,4,6-triamino propionic acid (L) in a heated condition.Ultimate analysis (C 12h 18n 6o 6) theoretical value: C42.10; H5.30; N24.55.Measured value: C42.04; H5.40; N24.53.
Another preferred embodiment of the present invention
1,3,5-triazines-2,4,6-triamino propionic acid (L) (0.1mmol) and Cu (Ac) 2h 2o (0.1mmol) filters stir half an hour in water (10mL) after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C 12h 21cuN 6o 8.5) theoretical value (%): C, 32.11; H, 4.72; N, 18.72.Measured value: C, 32.17; H, 4.74; N, 18.86.
The advantage and disadvantage that a kind of triazine propionic acid copper complex monocrystalline disclosed by the invention has is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) the triazine propionic acid copper complex monocrystalline prepared by the present invention, production cost is low, and method is easy, is applicable to scale operation.The photoelectric response range problem widening dyestuff can be solved at dyestuff or luminous agent application aspect.
Accompanying drawing explanation
Fig. 1: the crystalline structure figure of complex monocrystal;
Fig. 2: the one-dimensional catenary structure figure of complex monocrystal.
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.All raw material 1,3,5-triazines-2,4,6-triamines and 3-bromo-propionic acid etc. are all buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.
Embodiment 1
The preparation of 1,3,5-triazines-2,4,6-triamino propionic acid (L)
1,3,5-triazines-2,4,6-triamine: the mol ratio of 3-bromo-propionic acid is 1:4
In 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add 1,3,5-triazines-2,4,6-triamine (1mmol) and 3-bromo-propionic acid (4mmol) respectively, start and be stirred in 150 oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, the precipitation obtained is added 100mL hot methanol, after stirring and dissolving, filter, filtrate is slowly volatilized and is obtained white solid, yield 85%;
1,3,5-triazines-2,4,6-triamine 3-bromo-propionic acid.
The mol ratio of the present invention's preferred 1,3,5-triazines-2,4,6-triamine and 3-bromo-propionic acid is 1:4; Temperature of reaction 150 DEG C, 24 hours reaction times.Adopt " one kettle way ", 1,3,5-triazines-2,4,6-triamine and 3-bromo-propionic acid are prepared 1,3,5-triazines-2,4,6-triamino propionic acid (L) in a heated condition.Ultimate analysis (C 12h 18n 6o 6) theoretical value: C42.10; H5.30; N24.55.Measured value: C42.04; H5.40; N24.53.
Another preferred embodiment of the present invention
1,3,5-triazines-2,4,6-triamino propionic acid (L) (0.1mmol) and Cu (Ac) 2h 2o (0.1mmol) filters stir half an hour in water (10mL) after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C 12h 21cuN 6o 8.5) theoretical value (%): C, 32.11; H, 4.72; N, 18.72.Measured value: C, 32.17; H, 4.74; N, 18.86.
Embodiment 3
Crystal structure determination adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, unit cell parameters is obtained through least-squares refinement, software is utilized to solve crystalline structure from difference Fourier electron density map, 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:
Embodiment 4
The concrete instance that dyestuff or luminous agent use
Method: the PARSTAT2273 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 500W xenon lamp 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 USB4000plug-and-play Miniature optical linear light spectrometer.
Step: in order to definitely understand dyestuff at TiO 2adsorptive capacity on film, complex monocrystal dye sensitization TiO prepared by embodiment 2 2(geometric area is about 1cm to nanometer crystal film 2) be immersed in 10mL0.01molL -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 complex monocrystal is 1.4 × 10 -3mol/cm 2.
Result: compared with the methanol solution of dyestuff, complex monocrystal 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 complex monocrystal 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 500nm.
Embodiment 5
Triazine propionic acid copper complex monocrystalline is as the application preparing luminescent material.
Method: by spectrophotofluorometer, carries out the excitation wavelength of this compound monocrystal (embodiment 2) and the scanning of emission wavelength respectively, selects and determine optimal wavelength.
Conclusion: excitation wavelength and the emission wavelength of this compound are respectively 340nm and 500nm.
Step: triazine propionic acid copper complex monocrystalline grinding compressing tablet is become the sheet sample that external diameter is 27mm, thickness is about 3mm, and the sample pool putting into MPF-4 fluorescence spectrophotometer is measured.
Result: the excitation wavelength lambda of this compound ex=340nm, emission wavelength lambda em=500nm.
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 (3)

1. the monocrystalline of a triazine propionic acid copper complex, it is characterized in that this single crystal structure adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, unit cell parameters is obtained through least-squares refinement, software is utilized to solve crystalline structure from difference Fourier electron density map, and through Lorentz lorentz and polarizing effect correction, all H atom are synthesized by difference Fourier and are determined through desirable position calculation, thin axonometry data:
Its structure is as follows:
[CuL (H 2o)] 1.5H 2o, wherein
L=1,3,5-triazine-2,4,6-triamino propionic acid.
2. the preparation method of triazine propionic acid copper complex monocrystalline described in claim 1, is characterized in that it adopts normal temperature volatilization method, by L and Cu (Ac) 2h 2o filters stir half an hour in water after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:Cu (Ac) 2h 2the mol ratio of O is 1:1;
The structure of triazine propionic acid copper complex monocrystalline is [CuL (H 2o)] 1.5H 2o; Wherein L=1,3,5-triazine-2,4,6-triamino propionic acid;
L。
3. triazine propionic acid copper complex monocrystalline described in claim 1 is as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent.
CN201610001402.2A 2016-01-05 2016-01-05 Triazine copper propionate complex single crystal and preparation method and application thereof Pending CN105541873A (en)

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CN103059820A (en) * 2011-10-19 2013-04-24 中国石油化工股份有限公司 Non-aqueous coolant composition for engine
CN104151366A (en) * 2014-07-22 2014-11-19 南开大学 3d-4f heteronuclear metal-organic framework material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059819A (en) * 2011-10-19 2013-04-24 中国石油化工股份有限公司 Non-aqueous coolant composition for engine
CN103059820A (en) * 2011-10-19 2013-04-24 中国石油化工股份有限公司 Non-aqueous coolant composition for engine
CN104151366A (en) * 2014-07-22 2014-11-19 南开大学 3d-4f heteronuclear metal-organic framework material and preparation method thereof

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Application publication date: 20160504