CN1888969A - Method for producing isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials - Google Patents
Method for producing isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials Download PDFInfo
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- CN1888969A CN1888969A CN 200610088395 CN200610088395A CN1888969A CN 1888969 A CN1888969 A CN 1888969A CN 200610088395 CN200610088395 CN 200610088395 CN 200610088395 A CN200610088395 A CN 200610088395A CN 1888969 A CN1888969 A CN 1888969A
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Abstract
This is a method for preparing the isomorphic heteronuclear cubane metal cluster molecule functionality material. Lead sulfureted hydrogen into hartshorn of tungstenic acid or Sodium Molybdate and get 3-thio-ammonium tungstate and 3-thio-molybdate that is collected on a membrane filter by filtration under suction and desiccation. Add 3-thio-ammonium tungstate and 3-thio-molybdate into organic solvent, mix to entirely dissolve and get the 3-thio-ammonium tungstate and 3-thio-molybdate solution. Add cuprous halide into the mixture solvent of dimethylpyridine and volatile organic compounds solvent, mix to whole dissolution to get the cuprous halide solution. Drop 3-thio-ammonium tungstate or 3-thio-molybdate solution into cuprous halide solution with standing whisk.The reaction solution undergoes the heating, refluence, volatilization, crystal and desiccation to get the isomorphic heteronuclear cubane thio-metal cluster molecule function material. It can get the isomorphic heteronuclear cubane thio-metal cluster molecule functionality material that has signal conversion function of non-linearity refraction.
Description
One technical field
The present invention relates to the preparation of nonlinear optical material, especially a kind of preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal.
Two background technologies
The nonlinear optics functional material is a current domestic and international photoelectric information functional material research and a focus using focusing.These optical functional materialses not only can be applicable to the protection of photosensitive device and human eye; avoiding the injury of high-strength laser, but also can Application and Development in the modulation and the conversion of the reception of the transmission of photon communication, optical signalling and processing, optical data and storage, photoelectric functional, calculate until photon.Therefore, these third-order nonlinear optical functional materials have crucial researching value and wide application prospect at the laser instrument and the optical signalling technical elements in military and civilian field.Design and prepare the novel molecular functional materials with macro non-linear optical property, the optical property of researching and developing these functional materials then becomes an extremely important problem of current advanced material research and application.For example by three lithium borates (LBO) nonlinear optical crystal (the Chinese patent CN88102084.2 of Fujian Inst. of Matter Structure, Chinese Academy of Sciences invention, United States Patent (USP) 4,826,283, Jap.P. 2023845) large-scale production, product are mainly used in second harmonic (frequency multiplication and frequency tripling) and produce.
Transition metal sulphur is electronics and the architectural feature of cluster compound owing to the uniqueness that its molecule had: the diversity of bunch skeleton structure, modifiability and a bunch skeleton structure have comprised a plurality of heavy metal atoms, cause the diversity of the third order non-linear optical property that they showed and the difference of light limiting performance, made this metalloid cluster compound become the advanced optical credit subfunction material of a class novelty.Has one of function of significant application value as the third-order nonlinear optical functional material, the nonlinear refraction performance has two kinds of forms of self-focusing and self-defocusing, can be applicable to improve the light limiting performance of nonlinear optical material, avoid photosensitive device owing to being subjected to the damage that strong illumination causes, this nonlinear refraction performance also can be applicable to advanced all-optical switch preparation of devices exploitation simultaneously.Traditional representational third order non-linear optical material with nonlinear refraction performance comprises C
60And derivant, inorganic semiconductor, phthalocyanine and metal derivative thereof, organic conjugated molecule, superpolymer and metal simple-substance nano-cluster compound etc., B.Taheri (Appl.Phys.Lett.1996,68,1317) etc. has reported fullerene C
60The self-focusing performance, T.H.Wei (Appl.Phys.Lett.1998,72,2505) phthalocyanine and metal derivative nonlinear refraction thereof have been studied, L.Tapfer (Appl.Phys.Lett.1996,68,3820) Ag, non-linear and E.W.Van Stryland (the Semiconductors and Semimetals of Cu metal simple-substance nano-cluster compound refraction etc. have then been measured, 1999,58, (Nonlinear Optics in Semiconductors I), 257) etc. commented and the third-order non-linear refraction performance of having summed up inorganic semiconductor in 1999.Some transition metal sulphur are the cluster compound in recent years, for example straight chain type (H.G.Zheng et al, J.Chem.Soc.Dalton Trans.1997,2357), bird-nest type (H.W.Hou et al, Phys.Chem.Chem.Phys.1999,1,3145), half opening cubane type (S.Shi et al, Chem.Mater.1995,7,1519) and two bird-nest type (H.W.Hou et al, Inorg.Chem.1996,35,5363) be found and have very strong self-focusing or self-defocusing performance.But these metal cluster compounds of having reported can't overcome owing to nonlinear refraction cause from prism effect the damage to optical device that may cause, simultaneously because synthetic yield is low, the restriction of numerous factors such as accessory substance is many, synthesis condition harshness, causes above-mentioned metal cluster compound molecular functional materials to enter the practical stage and remain in certain difficulty.
Three summary of the invention
The object of the present invention is to provide a kind of preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal.
The technical solution that realizes the object of the invention is: a kind of preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials may further comprise the steps:
1.1 logical people reacts in the ammonia spirit of wolframic acid or sodium molybdate with hydrogen sulfide gas, makes three sulfo-ammonium tungstates or three sulfo-ammonium molybdates through suction filtration, drying;
1.2 the three sulfo-ammonium tungstates that make in the step 1.1 or three sulfo-ammonium molybdates are joined in the organic solvent stir, make the solution of three sulfo-ammonium tungstates or three sulfo-ammonium molybdates behind the CL;
1.3 cuprous halide is added in the mixed solvent of 2-picoline and volatile organic solvent, be stirred to the cuprous halide CL after, make the solution of cuprous halide;
1.4 the solution that contains three sulfo-ammonium tungstates or three sulfo-ammonium molybdates that obtains in the step 1.2 dropwise is added in the solution of the cuprous halide that obtains in 1.3 steps of not stopping stirring, makes the solution of isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
1.5 with the solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the step 1.4, reflux with nonlinear refraction function switching signal, and cold filtration, make the strong solution of isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
1.6 the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in the step 1.5 is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal.
Among the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials of the present invention, organic solvent comprises N, N '-dimethyl formamide, N, N '-dimethyl acetamide or N, N '-diethylformamide.
Among the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials of the present invention, the mol ratio of three sulfo-ammonium tungstates or three sulfo-ammonium molybdates and cuprous halide is 1: 2～3.5.
Among the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials of the present invention, 2-picoline and volatile organic solvent are by 55～75%: 25～45% percent by volume is carried out proportioning.
Among the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials of the present invention, cuprous halide comprises stannous chloride, cuprous bromide or cuprous iodide.
Among the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials of the present invention, volatile organic solvent comprises second eyeball, acetone or methylene chloride.
Among the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials of the present invention, the temperature of reflux is 50～60 ℃.
Among the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials of the present invention, the time of reflux is 1～2 hour.
The present invention compared with prior art, its remarkable advantage is: (1) not only can obtain to have the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal, and synthetic raw material is easy to get; (2) simple, the gentle easy control of process conditions of synthetic route; (3) the productive rate height of material, almost no coupling product; (4) chemistry of material, optical stability are good; (5) material possesses the nonlinear refraction function switching signal.
Four description of drawings
Accompanying drawing is the process flow diagram that the present invention has the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials preparation method of nonlinear refraction function switching signal.
Five embodiments
Below in conjunction with accompanying drawing the present invention is described in further detail.
In conjunction with the accompanying drawings, the present invention has the preparation method of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal, may further comprise the steps:
1.1 logical people reacts in the ammonia spirit of wolframic acid or sodium molybdate with hydrogen sulfide gas, makes three sulfo-ammonium tungstates or three sulfo-ammonium molybdates through suction filtration, drying;
1.2 the three sulfo-ammonium tungstates that make in the step 1.1 or three sulfo-ammonium molybdates are joined in the organic solvent stir, make the solution of three sulfo-ammonium tungstates or three sulfo-ammonium molybdates behind the CL;
1.3 cuprous halide is added in the mixed solvent of 2-picoline and volatile organic solvent, be stirred to the cuprous halide CL after, make the solution of cuprous halide;
1.4 the solution that contains three sulfo-ammonium tungstates or three sulfo-ammonium molybdates that obtains in the step 1.2 dropwise is added in the solution of the cuprous halide that obtains in 1.3 steps of not stopping stirring, makes the solution of isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
1.5 with the solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the step 1.4, reflux with nonlinear refraction function switching signal, and cold filtration, make the strong solution of isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
1.6 the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in the step 1.5 is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal.
Its specific embodiment is as follows:
Embodiment 1: the preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal of the present invention may further comprise the steps:
The first step is added to aqueous hydrochloric acid solution in the iron protosulfide and reacts, and the gas of generation makes hydrogen sulfide gas through the drying tower that molecular sieve is housed again through the safety flack of deionized water is housed;
Second goes on foot, and sodium molybdate is joined in the ammonia spirit stir, and makes the ammonia spirit of sodium molybdate;
The 3rd goes on foot, and reaction makes compound three sulfo-ammonium molybdates through suction filtration, drying in the sodium molybdate ammonia spirit that makes during the logical people to the second of sulfuretted hydrogen who makes in the first step is gone on foot;
The 4th step, take by weighing the three sulfo-ammonium molybdates that make in the 3rd step of 0.122 gram and join 4 milliliters of N, stir (N in N '-dimethyl formamide, N '-dimethyl acetamide or N, N '-diethylformamide all can), make the N of peony three sulfo-ammonium molybdates behind the CL, N '-dimethyl formamide solution;
The 5th step was added to 0.285 gram cuprous iodide in the mixed solvent of 6 milliliters of 2-picolines and 3 milliliters of second eyeballs (acetone or methylene chloride all can), be stirred to the cuprous iodide CL after, make the solution of glassy yellow cuprous iodide;
The 6th step, N with the peony three sulfo-ammonium molybdates that make in the 4th step, N '-dimethyl formamide solution dropwise is added in the solution of the glassy yellow cuprous iodide that makes in the 5th step that does not stop stirring, and makes the dark red solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
The 7th step, with 60 ℃ of the dark red solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the 6th step with nonlinear refraction function switching signal, refluxed 1 hour, and cold filtration, the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes with nonlinear refraction function switching signal.
The 8th goes on foot, and the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in going on foot the 7th is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that peony has the nonlinear refraction function switching signal.
Performance to the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal of present embodiment preparation detects as follows:
Nonlinear refraction performance test: use Np70 nanosecond/psec Nd:YAG laser system in 8 nanoseconds, test under the 532 nanometer conditions.
Optical property testing result by the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal of present embodiment preparation is listed in the following table.
Embodiment 2: the preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal of the present invention may further comprise the steps:
The first step is added to aqueous hydrochloric acid solution in the iron protosulfide and reacts, and the gas of generation makes hydrogen sulfide gas through the drying tower that molecular sieve is housed again through the safety flack of deionized water is housed;
Second goes on foot, and wolframic acid is joined in the ammonia spirit stir, and makes the ammonia spirit of wolframic acid;
The 3rd goes on foot, and reaction makes compound three sulfo-ammonium tungstates through suction filtration, drying in the wolframic acid ammonia spirit that makes during the logical people to the second of sulfuretted hydrogen who makes in the first step is gone on foot;
The 4th step, take by weighing the three sulfo-ammonium tungstates that make in the 3rd step of 0.166 gram and join 4 milliliters of N, stir (N in N '-dimethyl formamide, N '-dimethyl acetamide or N, N '-diethylformamide all can), make the N of orange-yellow three sulfo-ammonium tungstates behind the CL, N '-dimethyl formamide solution;
The 5th step was added to 0.190 gram cuprous iodide in the mixed solvent of 6 milliliters of 2-picolines and 3 milliliters of second eyeballs (acetone or methylene chloride all can), be stirred to the cuprous iodide CL after, make the solution of glassy yellow cuprous iodide;
The 6th step, N with the orange-yellow three sulfo-ammonium tungstates that make in the 4th step, N '-dimethyl formamide solution dropwise is added in the solution of the glassy yellow cuprous iodide that makes in the 5th step that does not stop stirring, and makes the orange-yellow solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
The 7th step, with 60 ℃ of the orange-yellow solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the 6th step with nonlinear refraction function switching signal, refluxed 1 hour, and cold filtration, the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes with nonlinear refraction function switching signal.
The 8th goes on foot, and the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in going on foot the 7th is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain orange-yellow isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal.
With embodiment 1, the result lists in the following table by the optical property detection method of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal of present embodiment preparation.
Embodiment 3: the preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal of the present invention may further comprise the steps:
The first step is added to aqueous hydrochloric acid solution in the iron protosulfide and reacts, and the gas of generation makes hydrogen sulfide gas through the drying tower that molecular sieve is housed again through the safety flack of deionized water is housed;
Second goes on foot, and sodium molybdate is joined in the ammonia spirit stir, and makes the ammonia spirit of sodium molybdate;
The 3rd goes on foot, and reaction makes compound three sulfo-ammonium molybdates through suction filtration, drying in the sodium molybdate ammonia spirit that makes during the logical people to the second of sulfuretted hydrogen who makes in the first step is gone on foot;
The 4th step, take by weighing the three sulfo-ammonium molybdates that make in the 3rd step of 0.122 gram and join 4 milliliters of N, stir (N in N '-dimethyl formamide, N '-dimethyl acetamide or N, N '-diethylformamide all can), make the N of peony three sulfo-ammonium molybdates behind the CL, N '-dimethyl formamide solution;
The 5th step was added to 0.190 gram cuprous iodide in the mixed solvent of 6 milliliters of 2-picolines and 3 milliliters of second eyeballs (acetone or methylene chloride all can), be stirred to the cuprous iodide CL after, make the solution of glassy yellow cuprous iodide;
The 6th step, N with the peony three sulfo-ammonium molybdates that make in the 4th step, N '-dimethyl formamide solution dropwise is added in the solution of the glassy yellow cuprous iodide that makes in the 5th step that does not stop stirring, and makes the dark red solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
The 7th step, with 60 ℃ of the dark red solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the 6th step with nonlinear refraction function switching signal, refluxed 1 hour, and cold filtration, the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes with nonlinear refraction function switching signal.
The 8th goes on foot, and the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in going on foot the 7th is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that peony has the nonlinear refraction function switching signal.
With embodiment 1, the result lists in the following table by the optical property detection method of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal of present embodiment preparation.
Embodiment 4: the preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal of the present invention may further comprise the steps:
The first step is added to aqueous hydrochloric acid solution in the iron protosulfide and reacts, and the gas of generation makes hydrogen sulfide gas through the drying tower that molecular sieve is housed again through the safety flack of deionized water is housed;
Second goes on foot, and wolframic acid is joined in the ammonia spirit stir, and makes the ammonia spirit of wolframic acid;
The 3rd goes on foot, and reaction makes compound three sulfo-ammonium tungstates through suction filtration, drying in the wolframic acid ammonia spirit that makes during the logical people to the second of sulfuretted hydrogen who makes in the first step is gone on foot;
The 4th step, take by weighing the three sulfo-ammonium tungstates that make in the 3rd step of 0.166 gram and join 4 milliliters of N, stir (N in N '-dimethyl formamide, N '-dimethyl acetamide or N, N '-diethylformamide all can), make the N of orange-yellow three sulfo-ammonium tungstates behind the CL, N '-dimethyl formamide solution;
The 5th step was added to 0.285 gram cuprous iodide in the mixed solvent of 6 milliliters of 2-picolines and 3 milliliters of second eyeballs (acetone or methylene chloride all can), be stirred to the cuprous iodide CL after, make the solution of glassy yellow cuprous iodide;
The 6th step, N with the orange-yellow three sulfo-ammonium tungstates that make in the 4th step, N '-dimethyl formamide solution dropwise is added in the solution of the glassy yellow cuprous iodide that makes in the 5th step that does not stop stirring, and makes the orange-yellow solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
The 7th step, with 60 ℃ of the orange-yellow solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the 6th step with nonlinear refraction function switching signal, refluxed 1 hour, and cold filtration, the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes with nonlinear refraction function switching signal.
The 8th goes on foot, and the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in going on foot the 7th is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain orange-yellow isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal.
With embodiment 1, the result lists in the following table by the optical property detection method of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal of present embodiment preparation.
Embodiment 5: the preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal of the present invention may further comprise the steps:
The first step is added to aqueous hydrochloric acid solution in the iron protosulfide and reacts, and the gas of generation makes hydrogen sulfide gas through the drying tower that molecular sieve is housed again through the safety flack of deionized water is housed;
Second goes on foot, and sodium molybdate is joined in the ammonia spirit stir, and makes the ammonia spirit of sodium molybdate;
The 3rd goes on foot, and reaction makes compound three sulfo-ammonium molybdates through suction filtration, drying in the sodium molybdate ammonia spirit that makes during the logical people to the second of sulfuretted hydrogen who makes in the first step is gone on foot;
The 4th step, take by weighing the three sulfo-ammonium molybdates that make in the 3rd step of 0.122 gram and join 4 milliliters of N, stir (N in N '-dimethyl formamide, N '-dimethyl acetamide or N, N '-diethylformamide all can), make the N of peony three sulfo-ammonium molybdates behind the CL, N '-dimethyl formamide solution;
The 5th step was added to 0.143 gram cuprous bromide in the mixed solvent of 6 milliliters of 2-picolines and 3 milliliters of second eyeballs (acetone or methylene chloride all can), be stirred to the cuprous bromide CL after, make the solution of glassy yellow cuprous bromide;
The 6th step, N with the peony three sulfo-ammonium molybdates that make in the 4th step, N '-dimethyl formamide solution dropwise is added in the solution of the glassy yellow cuprous bromide that makes in the 5th step that does not stop stirring, and makes the dark red solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
The 7th step, with 55 ℃ of the dark red solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the 6th step with nonlinear refraction function switching signal, refluxed 1.5 hours, and cold filtration, the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes with nonlinear refraction function switching signal.
The 8th goes on foot, and the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in going on foot the 7th is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that peony has the nonlinear refraction function switching signal.
Embodiment 6: the preparation method with isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials of nonlinear refraction function switching signal of the present invention may further comprise the steps:
The first step is added to aqueous hydrochloric acid solution in the iron protosulfide and reacts, and the gas of generation makes hydrogen sulfide gas through the drying tower that molecular sieve is housed again through the safety flack of deionized water is housed;
Second goes on foot, and wolframic acid is joined in the ammonia spirit stir, and makes the ammonia spirit of wolframic acid;
The 3rd goes on foot, and reaction makes compound three sulfo-ammonium tungstates through suction filtration, drying in the wolframic acid ammonia spirit that makes during the logical people to the second of sulfuretted hydrogen who makes in the first step is gone on foot;
The 4th step, take by weighing the three sulfo-ammonium tungstates that make in the 3rd step of 0.166 gram and join 4 milliliters of N, stir (N in N '-dimethyl formamide, N '-dimethyl acetamide or N, N '-diethylformamide all can), make the N of orange-yellow three sulfo-ammonium tungstates behind the CL, N '-dimethyl formamide solution;
The 5th step was added to 0.164 gram stannous chloride in the mixed solvent of 6 milliliters of 2-picolines and 3 milliliters of second eyeballs (acetone or methylene chloride all can), be stirred to the stannous chloride CL after, make the solution of glassy yellow stannous chloride;
The 6th step, N with the orange-yellow three sulfo-ammonium tungstates that make in the 4th step, N '-dimethyl formamide solution dropwise is added in the solution of the glassy yellow stannous chloride that makes in the 5th step that does not stop stirring, and makes the orange-yellow solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
The 7th step, with 50 ℃ of the orange-yellow solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the 6th step with nonlinear refraction function switching signal, refluxed 2 hours, and cold filtration, the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes with nonlinear refraction function switching signal.
The 8th goes on foot, and the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in going on foot the 7th is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain orange-yellow isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal.
Embodiment and fullerene C
60The nonlinear refraction performance parameter
| Laser frequency | Excited state amount of refraction (10 -22cm 3) | Ground state amount of refraction (10 -22cm 3) | The ratio of excited state amount of refraction and ground state amount of refraction | The nonlinear refraction performance | |
| Embodiment 1 | 10 nanoseconds | 0.70 | 1.17 | 0.6 | Self-defocusing |
| Embodiment 2 | 10 nanoseconds | 2.34 | 1.17 | 2.0 | Self-focusing |
| Embodiment 3 | 10 nanoseconds | 0.70 | 1.17 | 0.6 | Self-defocusing |
| Embodiment 4 | 10 nanoseconds | 2.34 | 1.17 | 2.0 | Self-focusing |
| Fullerene C 60 | 10 nanoseconds | 0.96 | 0.78 | 1.2 | Self-focusing |
Claims (8)
1, a kind of preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials may further comprise the steps:
1.1 logical people reacts in the ammonia spirit of wolframic acid or sodium molybdate with hydrogen sulfide gas, makes three sulfo-ammonium tungstates or three sulfo-ammonium molybdates through suction filtration, drying;
1.2 the three sulfo-ammonium tungstates that make in the step 1.1 or three sulfo-ammonium molybdates are joined in the organic solvent stir, make the solution of three sulfo-ammonium tungstates or three sulfo-ammonium molybdates behind the CL;
1.3 cuprous halide is added in the mixed solvent of 2-picoline and volatile organic solvent, be stirred to the cuprous halide CL after, make the solution of cuprous halide;
1.4 the solution that contains three sulfo-ammonium tungstates or three sulfo-ammonium molybdates that obtains in the step 1.2 dropwise is added in the solution of the cuprous halide that obtains in 1.3 steps of not stopping stirring, makes the solution of isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
1.5 with the solution heating of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials that makes in the step 1.4, reflux with nonlinear refraction function switching signal, and cold filtration, make the strong solution of isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal;
1.6 the strong solution of the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal that makes in the step 1.5 is placed on volatilization in the air, crystallization, filtration, washs, is drying to obtain the isomorphous heteronuclear cubane type sulfo-metal cluster compound molecular functional materials with nonlinear refraction function switching signal.
2, the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials according to claim 1 is characterized in that organic solvent comprises N, N '-dimethyl formamide, N, N '-dimethyl acetamide or N, N '-diethylformamide.
3, the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials according to claim 1 is characterized in that the mol ratio of three sulfo-ammonium tungstates or three sulfo-ammonium molybdates and cuprous halide is 1: 2～3.5.
4, the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials according to claim 1, it is characterized in that 2-picoline and volatile organic solvent are by 55～75%: 25～45% percent by volume is carried out proportioning.
5, the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials according to claim 1 is characterized in that cuprous halide comprises stannous chloride, cuprous bromide or cuprous iodide.
6, the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials according to claim 1 is characterized in that volatile organic solvent comprises second eyeball, acetone or methylene chloride.
7, the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials according to claim 1, the temperature that it is characterized in that reflux is 50～60 ℃.
8, the preparation method of isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials according to claim 1, the time that it is characterized in that reflux is 1～2 hour.
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| CN104722315A (en) * | 2015-04-07 | 2015-06-24 | 江南大学 | Preparation method for double-nest-shaped sulfo-metal cluster compound functional material with visible light catalysis performance |
| CN104741087A (en) * | 2015-03-30 | 2015-07-01 | 江南大学 | Preparation method of dual-plane five-core-shaped thio-metal cluster compound function material with visible light catalysis performance |
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| WO2024012473A1 (en) * | 2022-07-13 | 2024-01-18 | 苏州大学 | Tungsten/copper/sulfur cluster compound-based composite polymer film material, preparation method therefor, and use thereof in third-order nonlinear optics |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104741087A (en) * | 2015-03-30 | 2015-07-01 | 江南大学 | Preparation method of dual-plane five-core-shaped thio-metal cluster compound function material with visible light catalysis performance |
| CN104722315A (en) * | 2015-04-07 | 2015-06-24 | 江南大学 | Preparation method for double-nest-shaped sulfo-metal cluster compound functional material with visible light catalysis performance |
| CN104826660A (en) * | 2015-04-20 | 2015-08-12 | 江南大学 | Preparation method for sawtooth chain-shaped thio-metal cluster functional material with visible light catalytic performance |
| CN105622956A (en) * | 2016-03-17 | 2016-06-01 | 江南大学 | Method for preparing light-emitting crystal material [WS4Cu4(SCN)4Tb2(INA)4(HMPA)8]n with picric acid detecting function |
| CN105622956B (en) * | 2016-03-17 | 2018-03-02 | 江南大学 | Detectable picric luminescent crystal material [WS4Cu4(SCN)4Tb2(INA)4(HMPA)8]nPreparation method |
| WO2024012473A1 (en) * | 2022-07-13 | 2024-01-18 | 苏州大学 | Tungsten/copper/sulfur cluster compound-based composite polymer film material, preparation method therefor, and use thereof in third-order nonlinear optics |
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