CN105732646A - Sandwiched phthalocyanine rare-earth complex with two-photo absorption property and preparation method thereof - Google Patents
Sandwiched phthalocyanine rare-earth complex with two-photo absorption property and preparation method thereof Download PDFInfo
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- CN105732646A CN105732646A CN201610066213.3A CN201610066213A CN105732646A CN 105732646 A CN105732646 A CN 105732646A CN 201610066213 A CN201610066213 A CN 201610066213A CN 105732646 A CN105732646 A CN 105732646A
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 53
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 36
- -1 phthalocyanine rare-earth Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 29
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 28
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 172
- 239000000047 product Substances 0.000 claims description 81
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 80
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 239000002356 single layer Substances 0.000 claims description 34
- 239000012265 solid product Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 28
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 27
- 238000001953 recrystallisation Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 18
- SSVVHLRGCJLWCP-UHFFFAOYSA-N 4,5-dioctoxybenzene-1,2-dicarbonitrile Chemical compound CCCCCCCCOC1=CC(C#N)=C(C#N)C=C1OCCCCCCCC SSVVHLRGCJLWCP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000013500 data storage Methods 0.000 abstract description 4
- 238000002560 therapeutic procedure Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 65
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 26
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 25
- 238000004440 column chromatography Methods 0.000 description 24
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 22
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 12
- 238000000746 purification Methods 0.000 description 11
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- FGQSJRDKBCVFHH-UHFFFAOYSA-N erbium(3+) pentane-2,4-dione Chemical compound [Er+3].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O FGQSJRDKBCVFHH-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3619—Organometallic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
The invention belongs to the field of organic nonlinear optical materials, and particularly relates to a sandwiched phthalocyanine rare-earth complex with a two-photo absorption property and a preparation method thereof. The molecular structural formula of the sandwiched phthalocyanine rare-earth complex is as shown in the specification, wherein M is Y, Ho or Er. The complex has good solubility, stability and large two-photo absorption cross section and is expectably applied to the fields of two-photo photodyrnamic therapy, three-dimensional micro-manufacturing, two-photo optical amplitude limitation, three-dimensional optical data storage and the like.
Description
Technical Field
The invention belongs to the field of organic nonlinear optical materials, and particularly relates to a sandwich type phthalocyanine rare earth complex with two-photon absorption property and a preparation method thereof.
Background
Two-photon absorption is a nonlinear optical phenomenon, and is a process in which a medium absorbs two photons simultaneously through a virtual molecule under strong light excitation, and the medium transits from a ground state to an excited state with twice photon energy. The two-photon absorption material has important application prospects in the aspects of many modern high-tech fields such as three-dimensional micro-fabrication, two-photon dynamic therapy, two-photon light amplitude limiting, three-dimensional light data storage, fluorescence microscopic imaging and the like, and the development and development of novel two-photon absorption materials become one of the most active research fields in the world at present. Compared with other two-photon absorption materials, the organic two-photon absorption material has the advantages of low cost, easy device manufacturing and integration, adjustable performance through structural modification, high optical damage threshold, quick nonlinear optical response, larger nonlinear optical coefficient and the like.
The phthalocyanine is used as a multifunctional organic molecule, has a special two-dimensional conjugated pi-electron structure, has diversity and easy cutting property in the molecular structure, has higher stability to light and heat, has strong coordination capacity, and can be coordinated with most metal ions including rare earth elements, transition metals and main group elements to form a sandwich type complex. Compared with a single-layer phthalocyanine complex, the sandwich type complex has more excellent properties, and the material can be widely applied to the fields of organic field effect transistors, molecular information storage materials, monomolecular magnets and the like. In recent years, the application of sandwich type phthalocyanine rare earth complex as a third-order nonlinear optical material has received much attention. The reported complexes show higher second-order polarizability (gamma) values, the gamma values of the complexes are 1 to 2 orders of magnitude larger than those of typical single-layer phthalocyanines, and the complexes show good application prospects. The two-photon absorption cross section value is a key index for measuring a two-photon absorption material, and in order to improve the two-photon absorption cross section of phthalocyanine, people are constantly dedicated to synthesizing novel phthalocyanine derivatives and researching factors influencing the two-photon absorption property of the phthalocyanine derivatives. However, many studies have been made in this field almost focusing on single-layer phthalocyanine complexes, and reports on two-photon absorption properties of sandwich-type complexes have been rare.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a sandwich type phthalocyanine rare earth complex having excellent two-photon absorption properties and a preparation method thereof.
A sandwich type phthalocyanine rare earth complex with two-photon absorption property has a molecular structural formula as follows:
wherein M is Y, Ho or Er.
The preparation method of the sandwich type phthalocyanine rare earth complex with the two-photon absorption property comprises the following steps:
(1) heating and stirring hydrated acetylacetone rare earth salt, o-dicyanobenzene, n-amyl alcohol and a catalyst DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene) under the protection of nitrogen, cooling the obtained product, removing the solvent, dissolving the solid product in a small amount of chloroform, taking a chloroform-methanol solution as eluent, and purifying by using a silica gel chromatographic column to obtain a single-layer phthalocyanine rare earth complex;
(2) heating and stirring the monolayer phthalocyanine rare earth complex obtained in the step (1), 4, 5-dioctyloxy-o-dicyanobenzene, a catalyst DBU and n-amyl alcohol under the protection of nitrogen, cooling the obtained product, and recrystallizing and purifying to obtain the target product.
Wherein, the reaction equation is as follows:
the mole ratio of the acetylacetone rare earth salt hydrate to the ortho-dinitrile benzene in the step (1) is 1: 4-6.
The molar ratio of the single-layer phthalocyanine rare earth complex to the 4, 5-dioctyloxy-o-dicyanobenzene in the step (2) is 1: 4-6.
The heating reaction temperature in the step (1) is 100-120 ℃, and the stirring time is 2-4 hours.
The heating reaction temperature in the step (2) is 130-150 ℃, and the stirring time is 8-14 hours.
And (3) cooling the product obtained in the step (2), adding n-hexane for recrystallization, filtering the solid product, dissolving the solid product in a small amount of chloroform, purifying by using a chromatographic column, spraying the target product by using a chloroform-methanol solution, repeatedly passing through the column to purify the product, evaporating the solvent, recrystallizing by using a small amount of chloroform and n-hexane, filtering and drying to obtain the sandwich type phthalocyanine rare earth complex.
The invention provides three sandwich type phthalocyanine rare earth complexes (yttrium and holmium) with excellent two-photon absorption propertyErbium) with good solubility, stability and large two-photon absorption cross section, and the two-photon absorption cross section values of the two-photon absorption cross section values are respectively 1.28 × 10 under the femtosecond laser excitation with the wavelength of 800nm detected by adopting a Z scanning technology5GM (Y Yttrium), 1.26 × 105GM (Ho holmium) and 1.83 × 105GM (Er) is expected to be applied to the fields of two-photon kinetic therapy, three-dimensional micro-manufacturing, two-photon optical amplitude limiting, three-dimensional optical data storage and the like.
Drawings
FIG. 1 shows the UV-visible absorption spectrum (concentration 10) of a sandwich type yttrium phthalocyanine complex in chloroform solution-5mol/L)；
FIG. 2 shows the UV-visible absorption spectrum (concentration 10) of sandwich type holmium phthalocyanine complex in chloroform solution-5mol/L)；
FIG. 3 shows the UV-visible absorption spectrum (10% concentration) of sandwich type erbium phthalocyanine complex in chloroform solution-5mol/L)；
FIG. 4 is a Z-scan curve of a sandwich type yttrium phthalocyanine complex;
FIG. 5 is a Z-scan curve of a sandwich type holmium phthalocyanine complex;
FIG. 6 is a Z-scan plot of a sandwich-type erbium phthalocyanine complex.
Detailed Description
The invention is further explained below with reference to the figures and examples:
1. preparation of sandwich type yttrium phthalocyanine complex:
example 1
0.46g of yttrium acetylacetonate hydrate and 0.51g of o-dicyanobenzene were weighed out and placed in a sealed reactor, 5mL of n-pentanol and 12 drops of catalyst DBU were added, and the mixture was heated and stirred at 100 ℃ for 2 hours under the protection of nitrogen. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to obtain monolayer yttrium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 45 percent.
0.15g of monolayer yttrium phthalocyanine complex obtained in the step, 0.26g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol and heated to 150 ℃ under the protection of nitrogen for 10 hours. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type yttrium phthalocyanine complex is obtained with the yield of 42%.
Example 2
1g of yttrium acetylacetonate hydrate and 1.2g of o-dicyanobenzene are weighed into a sealed reactor, 10mL of n-amyl alcohol and 12 drops of catalyst DBU are added, and the mixture is heated and stirred for 2 hours at 100 ℃ under the protection of nitrogen. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to obtain monolayer yttrium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 35 percent.
0.5g of monolayer yttrium phthalocyanine complex obtained in the step, 0.9g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 10mL of n-amyl alcohol and heated to 150 ℃ under the protection of nitrogen for reaction for 10 hours. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type yttrium phthalocyanine complex is obtained with the yield of 32%.
Example 3
0.46g of yttrium acetylacetonate hydrate and 0.51g of o-dicyanobenzene were weighed out and placed in a sealed reactor, 5mL of n-pentanol and 12 drops of catalyst DBU were added, and the mixture was heated and stirred at 100 ℃ for 4 hours under the protection of nitrogen. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to obtain monolayer yttrium phthalocyanine complex. After repeated purification, the product was recrystallized from chloroform and n-hexane to obtain a pure product with a yield of 47%.
0.15g of monolayer yttrium phthalocyanine complex obtained in the step, 0.26g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol and heated to 150 ℃ under the protection of nitrogen for 14 hours. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type yttrium phthalocyanine complex is obtained with the yield of 44%.
Example 4
0.46g of yttrium acetylacetonate hydrate and 0.51g of o-dicyanobenzene were weighed out and placed in a sealed reactor, 5mL of n-pentanol and 12 drops of catalyst DBU were added, and the mixture was heated and stirred at 100 ℃ for 2 hours under the protection of nitrogen. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to obtain monolayer yttrium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 45 percent.
0.15g of monolayer yttrium phthalocyanine complex obtained in the step, 0.26g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol and heated to 150 ℃ under the protection of nitrogen for reaction for 8 hours. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type yttrium phthalocyanine complex is obtained with the yield of 38%.
2. Preparation of a sandwich type holmium phthalocyanine complex:
example 1
0.5g of holmium acetylacetonate hydrate and 0.61g of o-dicyanobenzene are weighed and placed in a sealed reactor, 5mL of n-amyl alcohol and a catalyst DBU10 are added, and the mixture is heated and stirred for 2 hours at 100 ℃ under the protection of nitrogen. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to form a monolayer holmium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 35 percent.
0.25g of the mono-layer holmium phthalocyanine complex obtained in the step above, 0.47g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol and reacted for 10 hours at 150 ℃ under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. And evaporating the solvent, recrystallizing with a small amount of chloroform and n-hexane, filtering, and drying to obtain the sandwich type holmium phthalocyanine complex with the yield of 25%.
Example 2
0.5g of holmium acetylacetonate hydrate and 0.61g of o-dicyanobenzene are weighed and placed in a sealed reactor, 5mL of n-amyl alcohol and a catalyst DBU12 are added, and the mixture is heated and stirred for 4 hours at 100 ℃ under the protection of nitrogen. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to form a monolayer holmium phthalocyanine complex. Repeatedly purifying, and recrystallizing with chloroform and n-hexane to obtain pure product with yield of 38%.
0.25g of the mono-layer holmium phthalocyanine complex obtained in the step above, 0.47g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol and reacted for 14 hours under reflux under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. And evaporating the solvent, recrystallizing with a small amount of chloroform and n-hexane, filtering, and drying to obtain the sandwich type holmium phthalocyanine complex with the yield of 27%.
Example 3
1g of holmium acetylacetonate hydrate and 1.2g of o-dicyanobenzene are weighed and placed in a sealed reactor, 5mL of n-amyl alcohol and a catalyst DBU12 are added, and the mixture is heated and stirred for 2 hours at 100 ℃ under the protection of nitrogen. After cooling, the n-pentanol is distilled off. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to form a monolayer holmium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 37 percent.
0.5g of the monolayer holmium phthalocyanine complex obtained in the step above, 0.85g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol and reacted for 10 hours under reflux under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. And evaporating the solvent, recrystallizing with a small amount of chloroform and n-hexane, filtering, and drying to obtain the sandwich type holmium phthalocyanine complex with the yield of 25%.
Example 4
0.5g of holmium acetylacetonate hydrate and 0.61g of o-dicyanobenzene are weighed and placed in a sealed reactor, 5mL of n-amyl alcohol and a catalyst DBU5 are added, and the mixture is heated and stirred for 2 hours at 100 ℃ under the protection of nitrogen. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed by chloroform methanol solution (chloroform: methanol: 95:5) to form a monolayer holmium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 34 percent.
0.25g of the mono-layer holmium phthalocyanine complex obtained in the step above, 0.47g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU5 are added dropwise into 5mL of n-amyl alcohol and reacted for 10 hours at 150 ℃ under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. And evaporating the solvent, recrystallizing with a small amount of chloroform and n-hexane, filtering, and drying to obtain the sandwich type holmium phthalocyanine complex with the yield of 23%.
3. Preparation of sandwich type erbium phthalocyanine complex:
example 1
0.25g of erbium acetylacetonate hydrate and 0.27g of o-dicyanobenzene are weighed into a sealed reactor, 5mL of n-amyl alcohol and 12 drops of catalyst DBU are added under the protection of nitrogen, and the mixture is heated and stirred for 2 hours at the temperature of 100 ℃. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed with chloroform methanol solution (chloroform: methanol: 95:5) to obtain a monolayer erbium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 33 percent.
0.15g of the single-layer erbium phthalocyanine complex obtained in the step, 0.26g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol, and the reflux reaction is carried out for 10 hours under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type erbium phthalocyanine complex is obtained with the yield of 21%.
Example 2
1g of erbium acetylacetonate hydrate and 1.1g of o-dicyanobenzene are weighed and placed in a sealed reactor, 10mL of n-amyl alcohol and 12 drops of catalyst DBU are added under the protection of nitrogen, and the mixture is heated and stirred for 2 hours at the temperature of 100 ℃. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed with chloroform methanol solution (chloroform: methanol: 95:5) to obtain a monolayer erbium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 32 percent.
0.6g of the single-layer erbium phthalocyanine complex obtained in the step, 1.05g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 10mL of n-amyl alcohol, and the reflux reaction is carried out for 10 hours under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type erbium phthalocyanine complex is obtained with the yield of 22%.
Example 3
0.25g of erbium acetylacetonate hydrate and 0.27g of o-dicyanobenzene were weighed out and placed in a sealed reactor, 5mL of n-pentanol and 12 drops of catalyst DBU were added under nitrogen protection, and the mixture was heated and stirred at 100 ℃ for 4 hours. The product is cooled and the n-pentanol is distilled out. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed with chloroform methanol solution (chloroform: methanol: 95:5) to obtain a monolayer erbium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 36 percent.
0.15g of the single-layer erbium phthalocyanine complex obtained in the step, 0.26g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU10 are added dropwise into 5mL of n-amyl alcohol, and the reaction is carried out under reflux for 14 hours under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type erbium phthalocyanine complex is obtained with the yield of 25%.
Example 4
0.25g of erbium acetylacetonate hydrate and 0.27g of o-dicyanobenzene are weighed into a sealed reactor, 5mL of n-amyl alcohol and 5 drops of catalyst DBU are added under the protection of nitrogen, and the mixture is heated and stirred for 2 hours at the temperature of 100 ℃. After cooling, the n-pentanol is distilled off. The solid product is dissolved in a small amount of chloroform, purified by a chromatographic column, and is sprayed with chloroform methanol solution (chloroform: methanol: 95:5) to obtain a monolayer erbium phthalocyanine complex. After repeated purification, the product is recrystallized by chloroform and normal hexane to obtain a pure product with the yield of 31 percent.
0.15g of the single-layer erbium phthalocyanine complex obtained in the step, 0.26g of 4, 5-dioctyloxy-o-dicyanobenzene and a catalyst DBU5 are added dropwise into 5mL of n-amyl alcohol, and the reflux reaction is carried out for 10 hours under the protection of nitrogen. After the product was cooled, 50mL of n-hexane was added to the reactor to carry out recrystallization, the solid product was dissolved in a small amount of chloroform after filtration, purified by a column chromatography, and the target product was poured with a chloroform-methanol solution (chloroform: methanol 99: 1). The product was purified by repeated column chromatography. After the solvent is evaporated, a small amount of chloroform and n-hexane are used for recrystallization, and after filtration and drying, the sandwich type erbium phthalocyanine complex is obtained with the yield of 20%.
4. Ultraviolet-visible spectrum of the sandwich type yttrium phthalocyanine complex:
FIG. 1 shows the UV-visible absorption spectrum of a sandwich type yttrium phthalocyanine complex in chloroform solution, and the absorption peaks of the complex at 335nm and 374nm can be identified as the Soret bands of phthalocyanine, while the strong absorption peak at 666nm can be identified as the Q band of phthalocyanine. The peak at 485nm is the characteristic absorption peak of the double-layer sandwich type rare earth complex.
FIG. 2 shows the UV-visible absorption spectrum of a sandwich type holmium phthalocyanine complex in chloroform solution, and the absorption peaks of the complex at 330nm and 365nm can be identified as the Soret band of phthalocyanine, while the strong absorption peak at 666nm can be identified as the Q band of phthalocyanine. The peak at 486nm is the characteristic absorption peak of the double-layer sandwich type rare earth complex.
FIG. 3 is the UV-visible absorption spectrum of a sandwich type erbium phthalocyanine complex in chloroform solution, and the absorption peaks of the complex at 327nm and 366nm can be identified as the Soret band of phthalocyanine, and the strong absorption peak at 667nm can be identified as the Q band of phthalocyanine. The peak at 487nm is the characteristic absorption peak of the double-layer sandwich type rare earth complex.
5. Two-photon absorption properties of the sandwich phthalocyanine rare earth complex:
the nonlinear absorption coefficient of the sandwich phthalocyanine rare earth complex is measured by using a Z scanning technology, and then a two-photon absorption cross section value is obtained. Among them, the two-photon absorption cross section is an important index for measuring the two-photon absorption property.
The light source used in the experiment is Ti sapphire laser produced by the United states Coherent companyThe wavelength of the device is 800nm, the pulse width is 170fs, the repetition frequency is 1000Hz, and the emergent Gaussian beam enters a sample after passing through a converging lens with the focal length of 15 cm. The thickness of the cuvette for the samples in the experiment is 2mm, and the radius w of the beam waist at the focus of the lens01.7mm, a Rayleigh wavelength of 20.09 μm, and a laser peak power I at the focal point of the lens0＝140GW/cm2The complex was dissolved in chloroform at a concentration of 1.1 × 10-3mol/L. The entire system was calibrated with cadmium sulfide crystals prior to measurement. In addition, chloroform, a pure solvent, was also measured under the same conditions to confirm that the peaks of the compounds measured all originated from the properties of the compounds without being affected by the solvent. The error range of the measurement is 20% up and down.
Fig. 4,5 and 6 are open-hole Z-scan experimental curves of a sandwich type yttrium phthalocyanine complex, a holmium phthalocyanine complex and an erbium complex respectively, and it can be seen from the graphs that the sample has strong nonlinear absorption, the normalized transmittance is reduced along with the increase of the incident light intensity, and the normalized transmittance is minimum (valley) near a focus. This nonlinear absorption is ascribed to two-photon absorption.
Fig. 4 to 6 were fitted with the formula (1) to obtain their two-photon absorption coefficients β.
T(z)＝1-0.33839ψ2+0.13326ψ2 2-0.03446ψ2 3+0.0377ψ2 4,(1)
Wherein,β two-photon absorption coefficient, I0Is the intensity of the gaussian light at the focal point,is the effective sample length, α0The two-photon absorption coefficients finally measured were β ═ 0.035cm/GW (yttrium complex), 0.033cm/GW (holmium complex) and 0.048cm/GW (erbium complex)The two-photon absorption cross section was found to be 1.28 × 105GM (Yttrium Complex), 1.26 × 105GM (holmium complex) and 1.84 × 105GM (erbium complex). Compared with most single-layer phthalocyanines, the two-photon absorption cross section value is 1-2 orders of magnitude higher, which indicates that the sandwich phthalocyanine rare earth complex is an excellent two-photon absorption material. The factor for improving the property of the compound is mainly that strong pi-pi interaction of phthalocyanine rings exists in the compound, so that the delocalization range of electrons is effectively improved, and the expansion of the delocalization range is an effective method for improving the nonlinear optical property of the compound. The phthalocyanine two-photon absorption material is expected to be applied to the fields of two-photon kinetic therapy, three-dimensional micro-manufacturing, two-photon light amplitude limiting, three-dimensional light data storage and the like.
Claims (7)
1. A sandwich type phthalocyanine rare earth complex with two-photon absorption property is characterized in that the molecular structural formula is as follows:
wherein M is Y, Ho or Er.
2. A method for preparing the sandwich type phthalocyanine rare earth complex with two-photon absorption property according to claim 1, which comprises the following steps:
(1) heating and stirring hydrated acetylacetone rare earth salt, o-dicyanobenzene, n-amyl alcohol and a catalyst DBU under the protection of nitrogen, cooling the obtained product, removing the solvent, dissolving the solid product in a small amount of chloroform, taking a chloroform-methanol solution as eluent, and purifying by using a silica gel chromatographic column to obtain a single-layer phthalocyanine rare earth complex;
(2) heating and stirring the monolayer phthalocyanine rare earth complex obtained in the step (1), 4, 5-dioctyloxy-o-dicyanobenzene, a catalyst DBU and n-amyl alcohol under the protection of nitrogen, cooling the obtained product, and recrystallizing and purifying to obtain the target product.
3. The method for preparing the sandwich-type phthalocyanine rare-earth complex with two-photon absorption property according to claim 2, wherein the molar ratio of the acetylacetone rare-earth salt hydrate to the ortho-dinitrile benzene in the step (1) is 1: 4-6.
4. The method for preparing a sandwich-type phthalocyanine rare-earth complex with two-photon absorption property according to claim 2, wherein the molar ratio of the monolayer phthalocyanine rare-earth complex to the 4, 5-dioctyloxy-o-dicyanobenzene in the step (2) is 1: 4-6.
5. The method for preparing a sandwich-type phthalocyanine rare-earth complex with two-photon absorption property as claimed in claim 2, wherein the heating reaction temperature in step (1) is 100-120 ℃, and the stirring time is 2-4 hours.
6. The method for preparing a sandwich-type phthalocyanine rare-earth complex with two-photon absorption property as claimed in claim 2, wherein the heating reaction temperature in the step (2) is 130-150 ℃ and the stirring time is 8-14 hours.
7. The method for preparing the sandwich-type phthalocyanine rare-earth complex with two-photon absorption property according to claim 2, wherein the product obtained in the step (2) is cooled, n-hexane is added for recrystallization, then the solid product is filtered and dissolved in a small amount of chloroform, the solid product is purified by a chromatographic column, a target product is sprayed by a chloroform-methanol solution, the product is purified by repeatedly passing through the column, the solvent is evaporated, the recrystallization is carried out by a small amount of chloroform and n-hexane, and the sandwich-type phthalocyanine rare-earth complex is obtained after filtering and drying.
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