CN116574055A - 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic and preparation method thereof - Google Patents
4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic and preparation method thereof Download PDFInfo
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- 230000005496 eutectics Effects 0.000 title claims abstract description 35
- -1 benzenesulfonic acid phenanthroline Chemical compound 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 42
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004080 punching Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- JIAGGSRRAAHALT-UHFFFAOYSA-N 4-[(8-hydroxyquinolin-5-yl)diazenyl]benzenesulfonic acid Chemical compound C12=CC=CN=C2C(O)=CC=C1N=NC1=CC=C(S(O)(=O)=O)C=C1 JIAGGSRRAAHALT-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001228 spectrum Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 239000000370 acceptor Substances 0.000 claims description 3
- 230000004323 axial length Effects 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 47
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic, the molecular formula is C 27 H 19 N 5 O 4 S, the structural formula isThe preparation method specifically comprises the following steps: (1) 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid, 1, 10-phenanthroline and a solvent are put into a reaction vessel together, and are placed on a stirrer for stirring under a closed condition to fully react; (2) Sealing the mouth of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing and volatilizingAnd (3) generating, namely, starting to precipitate red transparent blocky crystals in the reaction container. Compared with the dye, the dye eutectic is obviously improved in thermal stability, and the coplanarity of the crystal is enhanced due to the formation of the eutectic with the 1, 10-phenanthroline molecules, so that the fluorescence intensity of the eutectic is improved by nearly 8 times compared with the dye, and the problems of the original dye in stability and fluorescence intensity are greatly solved.
Description
Technical Field
The invention relates to the technical field of solid dye eutectic, in particular to a 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic and a preparation method thereof.
Background
In 1894, germany e.fischer proposed a "lock-key" model based on the idea of "intermolecular selectivity", i.e. a prototype of the modern supermolecular science theory. In 1937, K.L.Wolf et al, germany, created the term "supramolecule" to describe highly ordered entities formed by molecular association. In a general sense, any collection of molecules has interactions, so one often refers to the structural hierarchy of the material in an aggregated state as a "supermolecule". Until 1978, professor j.m.lehn in france eventually proposed the complete concept of "supermolecular chemistry" based on traditional guest-host system studies rooted in organic chemistry.
Supermolecular chemistry is the science of studying molecular aggregates that are complex and ordered and have specific structures and functions formed by the association of intermolecular interactions, which is "chemistry beyond the molecular domain", and such molecular aggregates are abbreviated as "supermolecules". Therefore, the basis of supermolecule chemistry is the science of intermolecular noncovalent interactions, which is a functional system formed by studying the noncovalent interactions between a plurality of different species of molecules.
Supermolecular chemistry has the following significant features: a. the strong binding force of the supermolecular compound is the result of superposition and synergy of weak interaction forces among different molecules, and is the comprehensive expression of various forces; b. supermolecular compounds self-assembled from different molecules exhibit novel functions that are completely different from those of the original self-assembled molecules. Molecular recognition and supramolecular self-assembly by synergism of weak intermolecular interactions are the core part of supramolecular chemistry studies.
The crystal engineering applies the principle and method of supermolecular chemistry to the design and growth of crystals, and obtains new crystals with adjustable structure and specific physicochemical properties through the combined action of molecular recognition and self-assembly processes. It is feasible to design dye eutectic routes by using crystal engineering theory, and the organic dye component and other eutectic precursors are connected through hydrogen bonds to form new crystals by using the crystal engineering theory. Organic dye components in crystalline form have traditionally been limited to their weak fluorescence intensity and poor thermal stability. The organic dye component itself has high application value in terms of intellectual property, wherein the structure and the constituent components are the most important constituent components. The Cambridge Structure Database (CSD) in the united kingdom is a major source of microscopic information about the structure of matter for molecular and material design.
Fluorescence is an important property of substances, playing a vital role in many technical fields, such as fluorescent tumor markers, OLEDs, etc. In some dyes, due to the structural characteristics and the characteristics of the functional groups, the dyes have certain fluorescent properties, and further have more applications. However, in the case of solid-state dyes, in the case of close packing, exciton coupling occurs between dye molecules to generate new exciton states, resulting in quenching of the fluorescent properties of the dye.
Therefore, how to maintain or enhance the fluorescence properties of solid-state dyes is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic and a preparation method thereof, so as to solve the defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
4- (8-hydroxy-5-quinolylazo) benzene sulfonic acid phenanthroline dye eutectic with molecular formula of C 27 H 19 N 5 O 4 S, the structural formula is
Furthermore, the 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic is prepared by taking 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid dye as an organic dye component and taking 1, 10-phenanthroline as a precursor through reaction;
wherein the molecular formula of the 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid is C 15 H 11 N 3 O 4 S, the structural formula is shown as a
The molecular formula of the 1, 10-phenanthroline is C 12 H 8 N 2 The structural formula is shown as b, is
The technical scheme has the beneficial effects that the azo compound 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid and the 1, 10-phenanthroline molecule form eutectic, so that the thermal stability is obviously improved compared with the dye. And the co-crystal is formed with 1, 10-phenanthroline molecules, so that the coplanarity of the crystal is enhanced, the fluorescence intensity of the co-crystal is improved by nearly 8 times compared with that of the dye, and the problems of poor thermal stability and weak fluorescence intensity of the original dye are greatly solved.
Further, the crystal structure of the 4- (8-hydroxy-5-quinolylazo) phenanthroline dye co-crystal is as follows: a1, 10-phenanthroline molecule and a 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid molecule are combined together through hydrogen bonds to form a basic structural unit.
Furthermore, in the above-mentioned 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid phenanthroline dye co-crystal, two N atoms (N9, N10) on one 1, 10-phenanthroline molecule act as hydrogen bond donors and two hydrogen bonds are formed with the N atom (N6) on quinoline in one 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid molecule as hydrogen bond acceptors.
Further, the space group of the 4- (8-hydroxy-5-quinolylazo) phenanthroline besylate dye eutectic is a triclinic system, and the unit cell parameters are as follows: the axial length a= 13.033-13.433, b= 13.642-14.042, c= 15.760-16.160; the shaft angle α= 72.350 to 72.750, β= 82.830 to 83.230, and γ= 74.670 to 75.070.
Further, XRD spectrum characteristic peaks of the 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid phenanthroline dye eutectic appear at 5.18-5.58 degrees, 12.66-13.06 degrees, 13.85-14.25 degrees, 14.77-15.17 degrees, 16.13-16.53 degrees, 17.41-17.81 degrees, 20.14-20.54 degrees, 23.23-23.63 degrees and 26.11-26.51 degrees. More specifically 5.38 °, 12.86 °, 14.05 °, 14.97 °, 16.33 °, 17.61 °, 20.34 °, 23.43 °, 26.31 °.
Further, the thermogravimetric curve of the 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid phenanthroline dye cocrystal under the air atmosphere test condition is as follows: the weight loss is 35-36% at 312-462 ℃, and then the material is completely decomposed at 497-745 ℃.
The preparation method (solvent room temperature volatilization method) of the 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic specifically comprises the following steps:
(1) 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid, 1, 10-phenanthroline and a solvent are put into a reaction vessel together, and are placed on a stirrer for stirring under a closed condition, and fully reacted to obtain red clear liquid;
(2) Sealing the mouth of the reaction container with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing for volatilization, and obtaining the 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic when red transparent blocky crystals begin to be separated out from the reaction container.
Further, in the step (1), the molar volume ratio of 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid, 1, 10-phenanthroline and solvent is (0.08-0.10) mmol (0.14-0.16) mmol (8-10) mL; the solvent is prepared by mixing ethanol, acetone and water in a volume ratio of 6:3:1; stirring time is 1-3 h.
The adoption of the further technical scheme has the beneficial effects that the boiling point of the solvent selected by the invention is relatively low, so that crystals are separated out in the process of volatilizing the solvent.
Further, in the step (2), the time of standing and volatilizing is 7 to 10 days.
Compared with the prior art, the invention has the following beneficial effects:
the solid quinoline azo fluorescent dye eutectic with the novel structure has obviously improved thermal stability compared with the dye, and the coplanarity of the crystal is enhanced due to the formation of the eutectic with the 1, 10-phenanthroline molecules, so that the fluorescence intensity of the eutectic is improved by nearly 8 times compared with the dye, and the problems of the original dye in stability and fluorescence intensity are greatly solved.
Drawings
FIG. 1 is a schematic diagram showing the structural units of phenanthroline 4- (8-hydroxy-5-quinolylazo) benzenesulfonate dye co-crystal prepared in example 1;
FIG. 2 is an XRD spectrum of the phenanthroline 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate dye co-crystal obtained in example 1 and an XRD spectrum obtained by simulation;
FIG. 3 is a thermogram of the phenanthroline 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate dye co-crystal obtained in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples below, the reaction vessel was a transparent glass vial, imported from a foreign country, and had a capacity of 20mL, and had a strong seal and maintained good tightness at temperatures below 120 ℃.
Example 1
The preparation method of the 4- (8-hydroxy-5-quinolyl azo) phenanthroline benzenesulfonate dye eutectic specifically comprises the following steps:
(1) Firstly, respectively measuring 6mL of ethanol, 3mL of acetone and 1mL of water in a 20mL transparent glass vial by using a 10mL pipette, and mixing to obtain a solvent; then 0.09mmol (30.00 mg) of 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid and 0.15mmol (27.00 mg) of 1, 10-phenanthroline which are accurately weighed by an analytical balance are added, and the mixture is placed on a stirrer under a closed condition to be stirred for 2 hours, and fully reacted to obtain red clarified liquid;
(2) Taking out the stirrer, sealing the opening of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing and volatilizing for 9 days, and obtaining the 4- (8-hydroxy-5-quinolylazo) phenanthroline benzenesulfonate dye eutectic after the red transparent blocky crystals begin to be separated out from the reaction vessel.
Example 2
The preparation method of the 4- (8-hydroxy-5-quinolyl azo) phenanthroline benzenesulfonate dye eutectic specifically comprises the following steps:
(1) Firstly, respectively measuring 6mL of ethanol, 3mL of acetone and 1mL of water in a 20mL transparent glass vial by using a 10mL pipette, and mixing to obtain a solvent; then 0.08mmol (26.00 mg) of 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid and 0.14mmol (25.00 mg) of 1, 10-phenanthroline which are accurately weighed by an analytical balance are added, and the mixture is placed on a stirrer under a closed condition to be stirred for 1 hour, and fully reacted to obtain red clarified liquid;
(2) Taking out the stirrer, sealing the opening of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing and volatilizing for 7 days, and obtaining the 4- (8-hydroxy-5-quinolylazo) phenanthroline benzenesulfonate dye eutectic after the red transparent blocky crystals begin to be separated out from the reaction vessel.
Example 3
The preparation method of the 4- (8-hydroxy-5-quinolyl azo) phenanthroline benzenesulfonate dye eutectic specifically comprises the following steps:
(1) Firstly, respectively measuring 6mL of ethanol, 3mL of acetone and 1mL of water in a 20mL transparent glass vial by using a 10mL pipette, and mixing to obtain a solvent; then 0.10mmol (33.00 mg) of 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid and 0.16mmol (29.00 mg) of 1, 10-phenanthroline which are accurately weighed by an analytical balance are added, and the mixture is placed on a stirrer under a closed condition to be stirred for 3 hours, and fully reacted to obtain red clarified liquid;
(2) Taking out the stirrer, sealing the opening of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing and volatilizing for 10 days, and obtaining the 4- (8-hydroxy-5-quinolylazo) phenanthroline benzenesulfonate dye eutectic after the red transparent blocky crystals begin to be separated out from the reaction vessel.
Performance testing
1. The structural unit of the phenanthroline 4- (8-hydroxy-5-quinolylazo) benzenesulfonate dye co-crystal obtained in example 1 was measured by using a Bruker Apex II CCD X-ray single crystal diffractometer (Bruker SMART-APEX CCD Diffractometer). The results are shown in FIG. 1.
As can be seen from FIG. 1, one 1, 10-phenanthroline molecule and one 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid molecule are bonded together by hydrogen bonds to constitute the basic structural unit. Wherein two N atoms (N9, N10) on one 1, 10-phenanthroline molecule are used as hydrogen bond donors, and two hydrogen bonds are formed by taking N atoms (N6) on quinoline in one 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid molecule as hydrogen bond acceptors.
The space group of the eutectic is a triclinic system, and the unit cell parameters are as follows: the axial length a= 13.033-13.433, b= 13.642-14.042, c= 15.760-16.160; the shaft angle α= 72.350 to 72.750, β= 82.830 to 83.230, and γ= 74.670 to 75.070.
2. The phenanthroline 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate dye co-crystal obtained in example 1 was used with X-Ray DIFFRACTOMETER (model XRD-6000, manufactured by Shimadzu corporation), cu-K.alphaThe XRD spectrum was measured at a tube voltage of 40kV, a tube current of 30mA, and a scanning speed of 8 DEG/min. And its XRD spectrum was simulated by Materials Studio software according to the crystal structure data. The results are shown in FIG. 2.
As can be seen from fig. 2, from the X-ray diffraction peaks (curve a) of the co-crystal, a series of characteristic peaks, more specifically, 5.38 °, 12.86 °, 14.05 °, 14.97 °, 16.33 °, 17.61 °, 20.34 °, 23.43 °, and 26.31 °, appear at 5.18 ° to 5.58 °,12.66 ° to 13.06 °,13.85 ° to 14.25 °,14.77 ° to 15.17 °,16.13 ° to 16.53 °,17.41 ° to 17.81 °,20.14 ° to 20.54 °,23.23 ° to 23.63 °, 26.11 ° to 26.51 °. Further, it was found by comparison that these characteristic peaks were coincident with the simulated X-ray diffraction spectrum peaks (curve b).
3. The thermal thermogram of the phenanthroline 4- (8-hydroxy-5-quinolylazo) benzenesulfonate dye co-crystal obtained in example 1 was measured using a thermal weight loss (TGA) and a Differential Thermal Analyzer (DTA) of SIMULTANNEOUS DTA-TG APPARATUS (model DTG-60, manufactured by Shimadzu corporation) at a heating rate of 10℃per minute under an air atmosphere. The results are shown in FIG. 3.
As can be seen from fig. 3, the thermogravimetric curve of the eutectic under the air atmosphere test conditions is: the weight loss is 35-36% at 312-462 ℃, and then the material is completely decomposed at 497-745 ℃.
4. The fluorescence intensities of the 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid and the prepared phenanthroline dye co-crystal of 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid in example 1 were measured respectively.
As a result, it was found that 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid was found to be present at lambda EX/EM Peak A at 302/326nm [ fluorescence intensity 42 (a.u.)]The method comprises the steps of carrying out a first treatment on the surface of the After forming 4- (8-hydroxy-5-quinolylazo) benzene sulfonic acid phenanthroline dye eutectic with 1, 10-phenanthroline molecule, lambda EX/EM Peak A at 306/332nm [ fluorescence intensity 328 (a.u.)]。
The experiment shows that the solid quinoline azo fluorescent dye eutectic with the novel structure has obviously improved thermal stability compared with the dye, and the eutectic is formed with 1, 10-phenanthroline molecules, so that the coplanarity of the crystal is enhanced, the fluorescence intensity of the eutectic is improved by nearly 8 times compared with the dye, and the problems of the original dye in stability and fluorescence intensity are greatly solved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A4- (8-hydroxy-5-quinolylazo) benzene sulfonic acid phenanthroline dye eutectic is characterized in that the molecular formula is C 27 H 19 N 5 O 4 S, the structural formula is
2. The 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid phenanthroline dye co-crystal according to claim 1, wherein the dye 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid is used as an organic dye component, and 1, 10-phenanthroline is used as a precursor, and the reaction product is obtained;
the molecular formula of the 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid is C 15 H 11 N 3 O 4 S, the structural formula is
The molecular formula of the 1, 10-phenanthroline is C 12 H 8 N 2 The structural formula is
3. The phenanthroline 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate dye co-crystal according to claim 2, wherein the crystal structure is: a1, 10-phenanthroline molecule and a 4- (8-hydroxy-5-quinolylazo) benzenesulfonic acid molecule are combined together through hydrogen bonds to form a basic structural unit.
4. The co-crystal of 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid phenanthroline dye according to claim 3, wherein two N atoms on one 1, 10-phenanthroline molecule act as hydrogen bond donors and form two hydrogen bonds with the N atoms on quinoline in one 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid molecule as hydrogen bond acceptors.
5. The co-crystal of 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid phenanthroline dye according to claim 1, wherein the space group is a triclinic system, and the unit cell parameters are: the axial length a= 13.033-13.433, b= 13.642-14.042, c= 15.760-16.160; the shaft angle α= 72.350 to 72.750, β= 82.830 to 83.230, and γ= 74.670 to 75.070.
6. The phenanthroline dye co-crystal 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate according to claim 1, wherein the XRD spectrum characteristic peaks appear at 5.18 ° to 5.58 °,12.66 ° to 13.06 °,13.85 ° to 14.25 °,14.77 ° to 15.17 °,16.13 ° to 16.53 °,17.41 ° to 17.81 °,20.14 ° to 20.54 °,23.23 ° to 23.63, 26.11 ° to 26.51 °.
7. The phenanthroline 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate dye co-crystal according to claim 1, wherein the thermogravimetric curve under air atmosphere test conditions is: the weight loss is 35-36% at 312-462 ℃, and then the material is completely decomposed at 497-745 ℃.
8. A method for preparing the phenanthroline dye co-crystal 4- (8-hydroxy-5-quinolylazo) benzenesulfonate according to claim 1, comprising the following steps:
(1) 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid, 1, 10-phenanthroline and a solvent are put into a reaction vessel together, and are placed on a stirrer for stirring under a closed condition, and fully reacted to obtain red clear liquid;
(2) Sealing the mouth of the reaction container by using tinfoil, punching a plurality of small holes on the tinfoil by using a needle, standing for volatilization, and obtaining the 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic when red transparent blocky crystals begin to be separated out from the reaction container.
9. The method for producing a phenanthroline dye co-crystal 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate according to claim 8, wherein in the step (1), the molar volume ratio of 4- (8-hydroxy-5-quinolinylazo) benzenesulfonic acid, 1, 10-phenanthroline and solvent is (0.08-0.10) mmol (0.14-0.16) mmol (8-10) mL; the solvent is prepared by mixing ethanol, acetone and water in a volume ratio of 6:3:1; the stirring time is 1-3 h.
10. The method for preparing a phenanthroline 4- (8-hydroxy-5-quinolinylazo) benzenesulfonate dye co-crystal according to claim 8, wherein in the step (2), the standing volatilization time is 7-10 days.
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