Method of forming a luminescent systems

 

(57) Abstract:

The invention is intended for the chemical industry and can be used to obtain materials for dosimetry, coverings for greenhouses and prevention materials for medicine. The black box was placed a solution containing 2 mmol (0,906 g) of terbium nitrate uranyl dissolved in 5 ml of distilled water. Add 4 mmol (0,792 g) 1,10-phenanthroline dissolved in ethanol, and 4 mmol (0,400 ml) of acetylacetone. Instead of the compounds of terbium is possible to use compounds of dysprosium. The ratio of the components in the box 1:1:2. The solution is stirred, covered with a filter KS-13, is placed under the lamp DXS-200. Irradiated for 8 h and the precipitate discarded raspberry pink color. The precipitate is filtered off, washed with water-ethanol mixture (1: 1), dried for 1 day. The composition of the obtained compound corresponds to the formula [Tb(NO3)2ASAS(Phen)2]H2), where ASAS - acetylacetonate ion, Phen is 1,10-phenanthroline. When using different filters adjust the spectral composition of radiation in the process of formation of donor-acceptor molecules. The best results were obtained in the wavelength range of the irradiation 480-2700 nm. The intensity of termomassazhnye compounds synthesized by irradiation of sunlight. 2 C.p. f-crystals, 1 tab., 2 Il.

The invention relates to luminescent materials, specifically, to create a luminous systems based donor-acceptor compounds which can be used as materials for dosimetry, as coverings for greenhouses, as therapeutic materials for medicine.

Luminous system is a system composed of donor-acceptor fragments, electronic structure which allows light rays to colonize unoccupied orbitals ("trap" electrons) with fixation of this phenomenon for quite a long time. Subsequent emptying of traps leads to recombination of charges, accompanied by release of light energy.

The known method of forming a luminescent systems through the creation of the molecular structure of the material with a spatial separation of separated charges within the same molecule. Under steady-state irradiation and the presence of the donor in such systems in the conditions of the experiment are able to accumulate anion-radical with a quantum yield of 10%. Such systems include, for example, covalently linked complex Ru(bpy)32+- viologen, where (bpy) - bipyridyl ("Photo is we have quite a large rate of recombination of separated charges, which up to the present time cannot be reduced.

The number of stored material energy characterized by the value of sutasoma, i.e., the amount of emitted light energy in the subsequent excitation of the material, which can be done in various ways. For example, to temperature effects (induced thermoluminescence - t), is the release of energy due to recombination "trap" States, caused by either physical or chemical causes.

It is known that the accumulation of energy occurs during the irradiation of some organic compounds (polyethylene, polystyrene, rubber, paraffin, cyclohexane, etc.) with fast electrons at 77 K. In this case, the generated positive and negative ions, which upon subsequent temperature treatment recombine, emitting light. Thus the value of sutasoma of such systems increases with increasing dose in the range of 1-5 Mrad (Alfimov M. C., Nicholas C. G. , Tambourine N. I.// Kinetics and catalysis. So 5, vol. 2. 1964. C. 268-276).

However, this method due to the use of ionizing radiation leads to rapid destruction of the source material.

It is known that in the donor-acceptor compounds separator), and due to the change of electronic structure of molecules of compounds formed by molecules of aromatic compounds having a large electron affinity and can exist in different electronic States: neutral, anion-radical and in the form of biradical (chemical factor) (C. Century. Lotnik, V. P. Kazakov, "Low-temperature chemiluminescence. M.: Nauka. 1987. S. 126; M. Magat // Int. J. Radiat. Phys. Chem. 1969, v. l, p. 199).

There are several ways of energy storage compounds due to changes in the number of trap States caused by such physical factors as, for example, increasing the number of defects in the crystal lattice.

For example, there is a method of creating a luminous systems by increasing the number of lattice defects in solids by annealing at a temperature of 450oC. in the annealed samples obtained crystallorophias is an increase in the intensity of the TL, as a measure of stored energy, in 1,5-2 times (Gurvich, A. M., Introduction to the physical chemistry of crystallorophias. M.: Higher school, 1982, S. 342-343).

Also known a method of creating a luminous system on the basis of the synthesis of compounds in the presence of activator, car, in an amount of 0.1 to 0.5 mol. %. The method leads to an increase in the number of defects in the crystal lattice (reducing energy "trap" state), i.e. to increase the value stored by the material energy, which is manifested in the increased intensity of thermoluminescence (TL) of these compounds. For example, adding as coactivator 0.2 mol. % of phosphorus, the intensity of the TL system BaS04- Eu increases 5 times (T. K. G. Rao, S. S. Shinde, B. C. Bhatt, J. K. Srivastava // J/Phys. Condens. Matter., 1995, p. 6569).

However, as a rule, the synthesis of such inorganic crystallorophias carried out at high temperatures and in strict compliance with the mass ratio of the luminescence centers and centers of fighting human trafficking, because the addition of a larger amount of the activator leads to a reduction in the number of "trap" States formed by physical defects, and causes suppression of THB (Gurvich, A. M., Introduction to the physical chemistry of crystallorophias. M.: Higher school, 1982, S. 120-142).

Closest to the claimed is a method of obtaining a luminescent system based donor-acceptor compounds, specifically, thermoluminescence complex compounds of rare earth element and a carboxylic acid type o, m or p-phthalic acid or the resulting material (century. C. Japan 57-80476, MKI 09 TO 11/46)

The value of the stored light energy of such compounds is determined by the electronic structure of donor-acceptor complexes formed after exposure to radiation. Thermoluminescent properties manifest themselves after the heat treatment of the obtained compound at temperatures around 250oC. it is noted that the influence of the light environment in the period between heat treatment and measurements of t does not affect the intensity of thermoluminescence.

It should be noted that in the literature it is not known how to create luminous systems based donor-acceptor compounds by increasing the number of "trap" conditions caused by chemical factors, i.e., by changing the electronic state of the molecules of the compounds in the process of their formation.

An object of the invention is the creation of a luminescent systems based donor-acceptor compounds by changing the number of "trap" States of molecules of donor-acceptor compounds in the process of their formation.

The problem is solved by a method of forming a luminescent systems on nirvanam light radiation in the process of formation of these compounds.

The method of obtaining the luminescent system is carried out by carrying out a reaction between the source components of the system in the conditions of irradiation with light of a specific wavelength.

For this purpose use light with a wavelength lying in the range from infrared (IR =2700 nm) to near ultraviolet (UVC, =200 nm).

This area of the light irradiation provides the transfer of electrons in the valence electron shells of atoms and molecules, which leads to a change in the process of synthesis of a number of "trap" States of molecules responsible for svetonakopitelnye.

Changing the composition of light, control the number of the "trap" States, i.e., control the amount of stored energy. The exposure time is determined by the time course of a particular chemical process.

First it is shown that the formation of molecules of donor-acceptor compounds in the context of differentiated light irradiation leads to the fact that depending on the wavelength of the used light emission of compounds of the same chemical composition changes and the number of stored energy, which is manifested by a change in the value of sutasoma terpolymers is but the use of the compounds, with the composition of the reaction center, donor and electron acceptor. For example, these compounds include ligand anion radical complexes of REE type [REE(NO3)2()(L)2] H20 or (REE)(A)3H2Oh, where as the cation-complexing agents (reaction center) is ion REE, mainly terbium or dysprosium; () (donor) - -diketones, such as acetylacetone, benzoylacetone, triflluoroacetylacetone, hexafluoroacetylacetone, benzoyltrifluoroacetone, thenoyltrifluoroacetone-acetone, dibenzoylmethane, dipivaloylmethane and others ; L (acceptor) is a nitrogen - containing heterocycles, such as 1.10-phenanthroline, 2.2' - dipyridyl and their derivatives, and aromatic acids such as benzoic acid, o-phthalic, m-phthalic, p-phthalic, hemimellitene, trimellitate, cinnamon, o-, m-, p-benzoic acid and others.

To create the required length mode is used or various filters, or a source of coherent light (lasers), or the corresponding lamp.

As filters, giving differentiated light radiation, use any filters, giving light in the field, responsible for svetonakopitelnye, for example, KS-13 (=620-2700 nm), th or lasers, working in the UV range (LIE-21, =337 nm) in the visible range (He-Ne, =633 nm) and infrared (Nd = 1064 nm) or lamp PDR-30 (max=254 nm), the TDR 250 (= 254-578 nm), DXS-200 (=290-2700 nm), etc.

In Fig.1 shows the curves of termomassazhnye sample [b(NO3)2ASAS(hn)2] H20, the resulting aqueous-alcohol synthesis in differentiated irradiation (1, 2, 3 and 5) and in normal conditions of solar illumination (4). Curve 1 describes the t of the sample obtained by irradiation through the optical filter with =620-2700 nm. Curve 2 by irradiation through the optical filter with = 1500-2700 nm. Curve 3 by irradiation through the optical filter with =480-2700 nm. Curve 4 is the same compound obtained under conditions of solar illumination, and curve 5 - termovision of the sample obtained when the exposure lamp CES-250 =254-578 nm.

In Fig.2 shows the curves of termomassazhnye connection [Tb(N03)2Acac(Phen)2] H20, obtained by solid-phase synthesis in differentiated radiation. Curves: 1 - filter KS-13 (620-2700 nm), 2 - solar light, 3 - light filter UFS-8 (365 nm) and 4 - mechanical mixture of the source compounds KNO3and b(ASAS)36N20.

Usually the synthesis of compounds with the ability to store light energy that prowl the ako, as the experiments showed, the trim during the synthesis of the spectral region from =200-480 nm, the intensity of thermoluminescence obtained under these conditions, compounds increases significantly. For example, when using the filter, X is 3 to 30%, and the COP-13 to 150%.

It was experimentally determined that irradiation of the reaction mixture with light in the spectral range 480-800 nm is observed a maximum increase in the number of stored energy, which manifests itself in increasing the intensity of thermoluminescence of the synthesized compounds, and at wavelengths 200-480 nm under conditions of severe exposure decreases the number of stored energy, and hence the reduction of thermoluminescence as a measure of stored energy. Apparently, the observed values of stored energy compounds from the spectral range of light radiation, where their education is associated with different efficiency effects of radiation on settling "trap" state of the synthesized complexes, and irradiation at =480-800 nm contributes to the appearance of the maximum number of "trap" States and, consequently, increase the intensity of thermoluminescence complexes.

Spectra luminoasa of thermostatted cell with temperature sensor and heater. The heating rate when thermophysical was Acting 3 K/s Spectra termomassazhnye were recorded using a standard amplifier on the basis of unit FL-BP, PMT-79 recording on dvukhkoordinatnyi the potentiometer. UV irradiation was carried out unfiltered light bulb CES-250, and the use of filters to generate light radiation of the same intensity required for subsequent comparison and analysis of results, used the lamp DXS-200.

The invention is illustrated by the following examples.

Example 1.

The black box was placed a solution consisting of 2 mmol (0,906 g) of terbium nitrate uranyl dissolved in 5 ml of distilled water, add 4 mmol (0,792 g) 1,10-phenanthroline dissolved in 15 ml of 96% ethanol and 4 mmol (0,400 ml) of acetylacetone. The ratio of initial components 1:2:2. The solution is stirred, covered with a filter KS-13, is placed under the lamp DXS-200 and irradiated for 8 hours and the precipitate discarded raspberry pink color. Turn off the lamp, take out of the box the reaction flask, the precipitate is filtered off, washed with 30 ml water-ethanol (1:1) mixture, and then dried for 1 day. Output 1,179 g (70%).

According to helices)2Acac(Phen)2]H20, where ASAS - acetylacetonate ion, Phen is 1,10-phenanthroline. Found/calculated: 47.75/45.72, N 3.40/3.9, N 10.17/9.95. The magnitude of sutasoma is 258% with respect to the sample obtained in normal conditions in the sunlight.

Examples 2-6 carried out analogously to example 1, changing only the light mode of synthesis, the terms of which are given in the table.

Example 7.

Carried out analogously to example 1, except that as the source used, the reaction mixture consisting of 2 mmol (0,879 g) of dysprosium nitrate uranyl dissolved in 5 ml of distilled water, to which is added 4 mmol (0,624 g), 2,2'-dipyridyl dissolved in 15 ml of 96% ethanol and 4 mmol (0,648 ml) benzoylacetone. The ratio of initial components 1: 2:2. The solution is placed under the lamp DXS-200, mix, cover with filter KS-3. Irradiated for 8 hours. Precipitated crystalline precipitate a pale yellow color filtered off, washed with 30 ml water-ethanol (1:1) mixture and dried for 1 day. Yield 1.2 g (70%).

According to chemical, x-ray uorescence analysis of the composition of the obtained compound corresponds to the formula [Dy(N03)2Bass(Dipy)2]H20, where the Bass - b is wearing the same sample, obtained under normal synthesis conditions on the sun light.

Conditions and results for examples 7-9 are shown in table.

Example 10.

Sample b(ASAS)3hn20,885 g u KNO30,202 g (molar ratio 1:2) are mixed and grinded in an agate mortar to sunlight. The mixing time 10 minutes Then the mixture is poured 10 ml of ethanol and shaken. The insoluble residue is filtered off and dried in air. Get 0,78 g of compound composition b(ASAS)(NO3)2hn2(yield 72%). The magnitude of sutasoma 100%.

Example 11.

Carried out analogously to example 10, except that the mixture is triturated under the lamp DXS-200 in the black box, the upper part of which is a filter KS-13. Output connection 70% (0,76 g). The magnitude of sutasoma 159% relative to example 10.

Example 12.

Analogously to example 11, but using the lamp CES-250 and the filter UFS-8. The output is 69% (0,80 g).

Example 13.

Carried out analogously to example 1, except that as the starting compound REE use a mixture 0,815 g of terbium nitrate uranyl and 0,088 g of dysprosium nitrate uranyl dissolved in 5 ml of d is the emotional components ratio 1:2:2. The compound obtained is a [Tbfor 0.9Dya 0.1(N03)2Acac(Phen)2]H20. The magnitude of sutasoma is 214%.

The table lists compounds, the synthesis of which was carried out with a water-alcohol method in terms of the effects of certain wavelengths (examples 1-9, 13) and in terms of solid-phase synthesis (examples 10-12), specified integrated intensity of termomassazhnye of the synthesized compounds on these same compounds synthesized under normal conditions, the intensity of which is taken as 100%.

As the table shows, the impact in the process of synthesis of light C =200-480 nm leads to a decrease of THB (example 5 and 12), i.e. to reduce the number of stored connection energy, while carrying out the synthesis under the influence of radiation from 480 nm to 2700 nm (examples 1-3, 6, 7, 9, 11, 13) increases the amount of stored energy, which is reflected in the strengthening of the TL, regarding the formation of such molecules in terms of solar radiation.

Thus, by adjusting the spectral content of the light emission during the formation of donor-acceptor molecules, it is possible to change the population "trap" States synthesized donor-acceptor to patelnie system, which can be used to create materials for photothermoelectric molecular photophysical and photochemical devices (detectors), utilizing solar energy by accumulation of charges in the trap of donor-acceptor groups in the interaction with the light rays.

The method can be used in the synthesis of new photothermoelectric systems based on metal-organic molecules that are used as components of molecular computer systems in molecular electronics and which are capable of molecular photoperiodicity when recharging the visible light of various wavelengths, as well as in Biophysics and biochemistry as model systems photoregulatory activity of phytochrome.

1. Method of forming a luminescent systems, including the formation of donor-acceptor compounds containing rare earth elements, and exposure to radiation, characterized in that the impacts are differentiated by light radiation in the process of formation of these compounds.

2. The method according to p. 1, characterized in that as the donor-acceptor compounds using ligand anion-radioassayed anion radical complexes of rare earth elements are used compounds of terbium and/or dysprosium.

 

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