CN114890914B - High-efficiency red light emitting organic crystal and application thereof in low-temperature fluorescence sensing - Google Patents
High-efficiency red light emitting organic crystal and application thereof in low-temperature fluorescence sensing Download PDFInfo
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Abstract
The invention discloses an organic high-efficiency red light emitting organic crystal with linear response to extremely low temperature and application thereof in low-temperature fluorescence sensing, belonging to the technical field of temperature sensing. The invention obtains a strong red light emitting organic crystal by a solvent volatilization method, the maximum emission wavelength of the crystal is 693nm, the fluorescence quantum efficiency is up to 73 percent, and the structural formula is shown as the formula (I). The invention also discloses application of the crystal emitting red light in low-temperature fluorescence sensing. Experiments prove that the maximum emission wavelength of the crystal has good linear response to extremely low temperature which is difficult to measure under the traditional condition, can sensitively react to temperature change at the extremely low temperature, and has wide application prospect in the aspect of low-temperature fluorescence sensing.
Description
Technical Field
The invention belongs to the technical field of temperature sensing, and particularly relates to a high-efficiency red light emitting organic crystal and application thereof in low-temperature fluorescence sensing.
Background
The temperature is one of important basic thermodynamic parameters, is closely related to the production life of people, and how to accurately measure the temperature under different conditions including a limit environment is always a problem which needs to be solved. The traditional temperature measurement principle is to measure the value of temperature according to volume, conductance and resistance change related to temperature, but from the practical application point of view, a temperature measurement instrument developed based on the principle cannot well meet the in-situ measurement required by industries such as micro-electro-mechanical systems, ocean research and aviation industry. Therefore, the temperature sensor which is suitable for carrying out in-situ measurement on the temperature in the extreme environment is developed, and the method has a very wide application prospect.
Since some fluorescent materials sensitive to temperature can respond well to temperature changes, temperature sensors based on fluorescent response are being developed to accurately detect temperature. The interest of researchers is mainly focused on the development of materials such as temperature sensitive luminescent organic dyes, polymers, nanocrystals and lanthanide series materials, which are somewhat less attractive for measurement under limited conditions, especially at very low temperatures. Due to the high price and low solubility of rare earth metals and the complexity of polymer and nanocrystal operation, attention is focused on luminescent organic dye small molecules sensitive to temperature, most of the organic dye fluorescence sensors reported at present are used for measuring the temperature in a solution or a polymer doped film, and the solution or the polymer doped film cannot effectively measure the temperature due to solidification and frost cracking at extremely low temperature. Therefore, there is an urgent need for an organic light-emitting small molecule fluorescence sensor that can measure extremely low temperatures.
Disclosure of Invention
Aiming at the defects of the existing low-temperature sensing material, the invention aims to provide a high-efficiency red light emitting organic crystal and application thereof in low-temperature fluorescence sensing.
The high-efficiency red light emitting organic crystal is simple in molecular structure, concise in synthesis steps and easy to crystallize, is prepared from a compound shown in a formula (I) through a solvent evaporation method, and is named as (2Z, 2 'Z) -3,3' - (2,5-bis (diphenylamino) -1,4-phenylene) bis (2- (4- (dibutylamino) phenyl) acrylonitrile) according to the specification.
The compound of formula (I) is prepared according to the following reaction formula:
aiming at the defect of the existing low-temperature fluorescent sensing material in the aspect of detecting the extremely low temperature, the invention develops the red light organic crystal which has higher fluorescent quantum efficiency and can accurately measure the extremely low temperature. The red light organic crystal prepared by the invention realizes stronger red light emission, which is very rare, because most of fluorescent molecules for red light emission are usually aggregated and induced to undergo fluorescence quenching particularly in a crystal state, so that the fluorescence quantum efficiency is greatly reduced, and stronger red light emission is difficult to realize. The efficient red light organic crystal prepared by the invention can realize stronger red light emission and can well measure extremely low temperature due to the special structure of the efficient red light organic crystal. At present, few literature reports on the realization of low-temperature accurate measurement of the high-efficiency red light organic crystal exist, and the high-efficiency red light emitting organic crystal has very wide application prospect for the detection of extremely low temperature due to the advantages.
Experimental results prove that the red light organic crystal sensitive to the extremely low temperature realizes high-efficiency red light emission due to the structural specificity, and the high-efficiency red light organic crystal is very easy to obtain due to the easy crystallinity of the organic molecule. The crystal overcomes the defect that the extremely low temperature cannot be accurately measured under the state of solution and film by the organic dye, provides a powerful tool for the organic dye in the field of low-temperature sensing, and more importantly, the design idea of the crystal can provide a general guidance for the design of high-efficiency red light crystals and extremely low-temperature sensing.
In a word, the extremely low temperature sensing material is a brand new red light organic crystal, compared with other temperature sensing materials, the crystal does not need redundant preparation processes, can realize high-efficiency red light emission, is relatively easy to detect the change of optical signals, has good linear response to the extremely low temperature which is difficult to measure under the traditional condition at the maximum emission wavelength, and can sensitively react to the temperature change under the extremely low temperature. In view of the advantages, the application of the fluorescent sensor in the aspect of low-temperature fluorescence sensing has wide prospects.
Drawings
FIG. 1: nuclear magnetic hydrogen spectrum of the organic fluorescent dye crystal prepared in example 1 of the present invention;
FIG. 2: nuclear magnetic carbon spectrum of the organic fluorescent dye crystal prepared in example 1 of the present invention;
FIG. 3: absorption (a) and emission spectrum (b) of the organic fluorescent dye crystal prepared in inventive example 1; the maximum emission wavelength of the crystal is 693nm, and the fluorescence quantum efficiency is as high as 73%;
FIG. 4: a structural analysis chart of the organic fluorescent dye crystal prepared in example 1 of the present invention; indicating that the obtained crystal is a triclinic system;
FIG. 5: optical photographs of the organic fluorescent dye crystal prepared in example 1 of the present invention under sunlight (a) and a 365nm ultraviolet lamp (b); the crystallinity of the crystal (-a in figure 5) and the high-efficiency red light luminescence property (-b in figure 5) are illustrated;
FIG. 6: the organic fluorescent dye crystal prepared in example 1 of the present invention has a fluorescence spectrum curve (-a in fig. 6, -b in fig. 6) of 77 to 295K and a curve (c in fig. 6) of the relationship between the ratio of the fluorescence intensity at 665nm and 697nm and the temperature change;
Detailed Description
Example 1: synthesis of (2Z,2 'Z) -3,3' - (2,5-bis (diphenylamino) -1,4-phenylene) bis (2- (4- (dibutylamino) phenyl) acrylonitrile)
To a two-necked flask were added 2- (4- (dibutylamino) phenyl) acetonitrile (153mg 0.626 mmol), 2,5-bis (diphenylamino) terephthalaldehyde (117mg, 0.250mmol), potassium tert-butoxide (71mg, 0.63mmol) and tetrabutylammonium hydroxide (214mg, 0.63mmol), further 10mL of tert-butanol and 5mL of tetrahydrofuran were added as solvents, and the resulting mixture was stirred at 50 ℃ for 4h. After cooling to room temperature, the mixture was poured into 50mL of methanol, the precipitate filtered and further purified by silica gel chromatography to give 177mg (0.200 mmol, 77%) of the product as a red-black solid, i.e. (2Z, 2 'Z) -3,3' - (2,5-bis (diphenylamino) -1,4-phenylene) bis (2- (4- (dibutylamino) phenyl) acrylonitrile).
10mg of the product was placed in a test tube, 5mL of dichloromethane was added to completely dissolve the compound, 10mL of petroleum ether solvent was slowly added to the dichloromethane solvent layer to separate the dichloromethane and petroleum ether layers, the tube mouth was sealed with cotton, and the red organic crystals were obtained by solvent evaporation. 1 H NMR(400MHz,CDCl3): δ7.86(s,2H),7.30–7.26(m,7H),7.25(s,3H),7.09(t,12H),6.97(t,J＝7.3Hz,4H),6.46(d,J＝8.5Hz,4H),3.24(t,8H),1.55–1.47(m,8H),1.39–1.26(m,8H),0.96(t, 12H). 13 C NMR (101MHz, CDCl3): delta 148.65,147.62,143.24,134.33,132.72,129.54, 129.41,127.08,122.65,122.49,120.63,117.56,113.88,111.16,50.64,29.34,20.28,13.96. Unit cell parameters in the crystal a =8.4810 (3), b =11.4818 (5), c =14.0570 (6), α =89.7366 (15), β =87.7218 (16), γ =86.1781 (15), triclinic. Fig. 1, fig. 2, fig. 4 and the above data indicate that the structural product was obtained.
Example 2: measurement of absorption and emission spectra of the organic crystals prepared in example 1
The crystals obtained in example 1 were dispersed on a barium sulfate substrate, and an absorption spectrum was obtained by scanning with an ultraviolet-visible spectrophotometer at a wavelength band of 300 to 900 nm. The fluorescence emission spectrum was obtained by scanning with a fluorescence spectrometer under 405nm excitation, and the two sets of data were plotted with Origin software to obtain the absorption-emission spectrum (absorption spectrum in the left part and emission spectrum in the right part) of the organic crystal shown in FIG. 3. The absorption-emission peak position of the red organic crystal and its large stokes shift are illustrated.
Example 3: temperature swing (77-295K) fluorescence test of organic crystals prepared in example 1
The crystal obtained in example 1 was sampled, placed in a chamber containing the sample, 77K liquid nitrogen was poured into a cooling device, the crystal sample was excited using a 375nm LED excitation light source, the fluorescence emission spectra were collected, and then the fluorescence emission spectra were collected once every 20K increase by programmed temperature increase by a control system. Processing the data by Origin software to obtain the temperature-changing (77-295K) fluorescence test result of the crystal as shown in fig. 6, wherein (a) in fig. 6 is 175-295K (the intensity of the fluorescence emission peak is weakened along with the rise of the temperature), and (b) in fig. 6 is 77-175K (the intensity of the fluorescence emission peak at 665nm is weakened along with the rise of the temperature, and the intensity of the fluorescence emission peak at 697nm is strengthened); c in FIG. 6 is a plot of fluorescence intensity ratio at 665nm and 697nm in a in FIG. 6 and b in FIG. 6, versus temperature change, as data processed by Origin software (equation y =1.37-0.00689x 2 =0.9999, wherein y represents the ratio of fluorescence intensities at 665nm and 697nm, and x represents the temperature). And further measuring the fluorescence emission spectrum of the red organic crystal at unknown ambient temperature, calculating the fluorescence intensity ratio at 665nm and 697nm, substituting the ratio into the relation curve, and calculating to obtain the ambient temperature, thereby realizing the accurate measurement in the low temperature (77-175K) range.
Claims (3)
1. A red light-emitting organic crystal prepared from a compound represented by formula (I) by a solvent evaporation method is a triclinic system, and the unit cell parameters in the crystal are a =8.4810 (3), b =11.4818 (5), c =14.0570 (6), α =89.7366 (15), β =87.7218 (16), γ =86.1781 (15),
2. use of a red-emitting organic crystal according to claim 1 in low temperature fluorescence sensing.
3. Use of a red-emitting organic crystal according to claim 2 in low temperature fluorescence sensing, wherein: the low-temperature sensing range is 77-175K.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104927841A (en) * | 2015-06-17 | 2015-09-23 | 太原理工大学 | Near infrared organic fluorescent dye with mechanical responsiveness |
| CN109957395A (en) * | 2019-04-10 | 2019-07-02 | 济宁学院 | A kind of thermally sensitive light-emitting semiconducting material and its preparation method and application |
| CN110483381A (en) * | 2019-09-11 | 2019-11-22 | 天津理工大学 | A kind of preparation method and application of the near infrared fluorescent compound of solid-state soda acid stimuli responsive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104927841A (en) * | 2015-06-17 | 2015-09-23 | 太原理工大学 | Near infrared organic fluorescent dye with mechanical responsiveness |
| CN109957395A (en) * | 2019-04-10 | 2019-07-02 | 济宁学院 | A kind of thermally sensitive light-emitting semiconducting material and its preparation method and application |
| CN110483381A (en) * | 2019-09-11 | 2019-11-22 | 天津理工大学 | A kind of preparation method and application of the near infrared fluorescent compound of solid-state soda acid stimuli responsive |
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