CN107759775A - The condensed cyclic structure containing sulfuryl gives receptor type alternating polymer, preparation method and application with strong two-photon effect - Google Patents
The condensed cyclic structure containing sulfuryl gives receptor type alternating polymer, preparation method and application with strong two-photon effect Download PDFInfo
- Publication number
- CN107759775A CN107759775A CN201710992465.3A CN201710992465A CN107759775A CN 107759775 A CN107759775 A CN 107759775A CN 201710992465 A CN201710992465 A CN 201710992465A CN 107759775 A CN107759775 A CN 107759775A
- Authority
- CN
- China
- Prior art keywords
- photon
- cyclic structure
- condensed cyclic
- strong
- receptor type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *c1c(c2ccccc2[s]2)c2c(*)c2c1[s]c1ccccc21 Chemical compound *c1c(c2ccccc2[s]2)c2c(*)c2c1[s]c1ccccc21 0.000 description 3
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
- C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
- C08G2261/522—Luminescence fluorescent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a kind of condensed cyclic structure containing sulfuryl receptor type alternating polymer and preparation method and application is given with strong two-photon effect.Preparation method of the present invention is using condensed cyclic structure containing sulfuryl as short of electricity subbase group, reasonable selection electron rich group, and receptor type alternating polymer is given with strong two-photon effect by a kind of obtained described condensed cyclic structure containing sulfuryl of Suzuki polymerisations.The condensed cyclic structure containing sulfuryl of the present invention has strong single photon fluorescence and two-photon fluorescence intensity to receptor type alternating polymer, there is good dissolubility simultaneously, it can be dissolved in conventional organic solvent, it is easy to the test and application of two-photon absorption performance, in non-linear optical field tool actual application value.
Description
Technical field
The invention belongs to two-photon fluorescence polymer arts, and in particular to a kind of condensed cyclic structure containing sulfuryl has strong double light
Sub- effect gives receptor type alternating polymer and preparation method and application.
Background technology
Goppert-Mayer in 1931 take the lead in proposing the concept of two-photon absorption, and theoretically calculate two-photon
The transition probability of process.Material (is represented, V by middle virtual stake in the presence of strong light (such as laser) in Fig. 1 with V1, V2Can wait can
Absorb not equally) and simultaneously energy (the hv of two photons1+hv2) after, from ground state S0Transit to excitation state Sn(SnEnergy level is two light
Son energy) process be referred to as two-photon absorption (TPA).Between the limitation of experiment condition, until going out for laser at the beginning of the sixties
It is existing, Kaiser just in an experiment first observed to this phenomenon, it was confirmed that Goppert-Mayer prophesy.Two-photon absorption is
A kind of nonlinear optical phenomena, with the rapid advances of laser technology, researchers are more and more deeper to probing into for two-photon absorption
Enter, it is broadly extended to three-dimensional information storage, two-photon up-conversion lasing, double light except being a kind of spectral results
Son absorbs the fields such as optical Limiting, two-photon fluorescence microscope, photodynamic therapy.
Most important with strong two-photon absorption material be characterised by molecular structure with larger conjugated system and
Stronger gives/electron-withdrawing power.Sulfuryl is a kind of strong short of electricity subbase group, uses it for building polynary condensed cyclic structure, can not only make
New unit retains sulfuryl electrophilic function by force, is introduced into strand, can show strong Intramolecular electron transfer effect；And
And multi-factor structure assigns the preferable flatness of new unit and rigidity so that new unit has higher fluorescence quantum yield.Sulfuryl
Presence have two-photon response beneficial to polymeric material.
The content of the invention
To solve the shortcomings that prior art and weak point, primary and foremost purpose of the invention is to provide a kind of condensed ring containing sulfuryl
Structure gives receptor type alternating polymer with strong two-photon effect.The polymer is the polymer containing sulfuryl of D-A type, is had
There is the feature of preferable dissolubility, higher fluorescence quantum yield and strong two-photon response.
Another object of the present invention is to provide a kind of described condensed cyclic structure containing sulfuryl to have strong two-photon effect
Preparation method to receptor type alternating polymer.This method is using condensed cyclic structure containing sulfuryl as short of electricity subelement, selection and electron deficient
The electron rich unit that unit matches, it is strong that a kind of having for described condensed cyclic structure containing sulfuryl is made by Suzuki polycondensation reactions
Two-photon effect gives receptor type alternating polymer.
There is strong two-photon effect it is still another object of the present invention to provide a kind of described condensed cyclic structure containing sulfuryl
Application to receptor type alternating polymer.
The object of the invention is achieved through the following technical solutions：
A kind of condensed cyclic structure containing sulfuryl gives receptor type alternating polymer, its structural formula such as formula with strong two-photon effect
(1) shown in：
In formula, A is short of electricity subelement, and D is electron rich unit.
Described short of electricity subelement A structure is any one in following structure：
In above-mentioned short of electricity subelement A preferred structure formula, R is selected from H, C1~C30Straight chain or branched alkyl,AndR3Selected from H, C1~C30Straight chain or branched alkyl and C1~C30Alcoxyl
Base.
The electron rich cells D is any one in following structural formula：
In the preferred structure formula of above-mentioned electron rich cells D, R is selected from H, C1~C30Straight chain or branched alkyl,AndR3Selected from H, C1~C30Straight chain or branched alkyl and C1~C30Alcoxyl
Base；
R1、R2、R4~R7Can be identical or different it be independently selected from H, C1~C30Straight chain or branched alkyl, C1~C30's
Alkoxy,AndR8Selected from H, C1~C30Straight chain or branched alkyl and C1~
C30Alkoxy.
A kind of preparation to receptor type alternating polymer with strong two-photon effect of described condensed cyclic structure containing sulfuryl,
Essentially consist in the synthesis of short of electricity subelement A and electron rich cells D.
A kind of preparation to receptor type alternating polymer with strong two-photon effect of described condensed cyclic structure containing sulfuryl,
It is to polymerize to obtain by Suzuki with electron rich cells D by the A of condensed cyclic structure containing sulfuryl.
Further, a kind of described condensed cyclic structure containing sulfuryl there is strong two-photon effect to give receptor type alternating polymerization
The preparation method of thing, comprises the following steps：
(1) under inert gas atmosphere, sulfuryl condensed cyclic structure monomer A, electron rich cells D are dissolved with toluene, add palladium
With thricyclohexyl phosphorus and the tetraethyl ammonium hydroxide aqueous solution, heating stirring, temperature is reacted 24~36 hours at 60~110 DEG C；
(2) phenyl boric acid end-blocking is added, continues reaction 6~12 hours；Bromobenzene end-blocking is added, continues reaction 6~12 hours；
(3) after polymerization terminates, reaction solution precipitating in methyl alcohol, filtering, extracted successively with methanol, acetone and n-hexane, then
Using toluene as eluent, silicagel column carries out column chromatography, concentration, and precipitating in methanol solution, filters again, dries, obtains institute
State the condensed cyclic structure containing sulfuryl have strong two-photon effect to receptor type alternating polymer.
Further, inert gas includes argon gas described in step (1)；
Further, the mol ratio of short of electricity subelement A described in step (1) and electron cells D is 1:1；
Further, the palladium described in step (1), thricyclohexyl phosphorus and short of electricity subelement A mol ratio are 1：
2：100~150；
Further, the volume ratio of the tetraethyl ammonium hydroxide aqueous solution described in step (1) and toluene is 1:6~
10。
Further, the phenyl boric acid described in step (2)：Bromobenzene：The mol ratio of short of electricity subelement is 0.2~0.5：2
~5：1.
A kind of described condensed cyclic structure containing sulfuryl gives receptor type alternating polymer non-thread with strong two-photon effect
Application in property optical field, is included in two-photon fluorescence microtechnic, two-photon up-conversion lasing, optical Limiting, two-photon three
Tie up the application of processing, double photon three dimension optical storage, double-photon optical photodynamic therapy etc..
Further, in application process, the condensed cyclic structure containing sulfuryl has being handed over to receptor type for strong two-photon effect
Power for the two-photon absorption performance of polymer is weighed with two photon absorption cross section, and two photon absorption cross section value is bigger, contains
The two-photon absorption ability of the compound of S, S- dioxo-dibenzothiophene unit is stronger, and response is faster.
Further, the test mode of the two photon absorption cross section is：By the containing with strong two-photon effect
Sulfuryl condensed cyclic structure is dissolved to receptor type alternating polymer with organic solvent, then is scanned by two-photoninduced fluorescence method, Z-
Technology, nonlinear transmission method or the test of two-photon transient absorption spectra method.
Further, the organic solvent include toluene, dimethylbenzene, n-hexane, ether, dioxane, dichloromethane,
Chloroform, ethyl acetate, tetrahydrofuran, 1,2- dichloroethanes, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, third
Ketone, dimethyl sulfoxide (DMSO) or chlorobenzene.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) the giving in receptor type alternating polymer with strong two-photon effect of the condensed cyclic structure containing sulfuryl of the invention, sulfone
Base is strong short of electricity subbase group, and electronegativity is stronger than fluorine, ester group, carbonyl etc., therefore, the unit electrophilic energy of the condensed cyclic structure containing sulfuryl
Power is strong, and Intramolecular electron transfer effect is strong between the electron rich unit being attached thereto, and can increase substantially the two-photon of polymer
Absorb response.
(2) condensed cyclic structure containing sulfuryl of the invention there is strong two-photon effect give receptor type alternating polymer, due to
With larger conjugate length, so there is higher fluorescence quantum yield, be advantageous to strengthen the two-photon absorption ability of compound.
(3) condensed cyclic structure containing sulfuryl of the invention with strong two-photon effect to receptor type alternating polymer with by force
Single photon fluorescence and two-photon fluorescence intensity, while there is good dissolubility, can be dissolved in conventional organic solvent, be easy to
The test and application of two-photon absorption performance, in non-linear optical field tool actual application value.
Brief description of the drawings
Fig. 1 is two-photon absorption (TPA) energy diagram；
Fig. 2 is single photon fluorescence spectrogram of the polymer P 1 in opposed polarity solvent；
Fig. 3 is two-photon fluorescence spectrogram of the polymer P 2 in toluene solution under different optical maser wavelengths；
Fig. 4 is the graph of a relation of two photon absorption cross section and optical maser wavelength of the polymer P 1 in opposed polarity solvent；
Fig. 5 is the graph of a relation of two photon absorption cross sections and optical maser wavelength of the 2~P4 of polymer P in toluene solution.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.It should be appreciated that appended claims summarise the scope of the present invention, and under the guiding of present inventive concept, the skill of this area
Art personnel will be appreciated that the change carried out to various embodiments of the present invention, all by by the spirit of claims of the present invention
Covered with scope.
Embodiment 1：The synthesis of the hexyloxy benzene of 1,4- bis-
Under argon gas protection, added into 500ml two-mouth bottle to biphenol (11g, 0.10mol), TBAB
(0.32g, 1.00mmol), 50wt% sodium hydrate aqueous solution (20g/20ml deionized waters, 0.5mmol) and toluene solvant
(200ml).Heating stirring, when temperature stabilization is to 80 DEG C, add n-hexyl bromine (36.31g, 0.22mmol).Reaction 6 hours
Afterwards, terminating reaction, organic layer is separated, concentration, for crude product by the Methods For Purification of column chromatography, petroleum ether is eluant, eluent, final to obtain
To 25.1g white solids, yield 91%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target
Product, chemical equation are as follows：
Embodiment 2：The synthesis of the bromo- hexyloxy benzene of 2,5- bis- of 1,4- bis-
Under the conditions of lucifuge, into 250ml stand up reaction bottle add the hexyloxy of Isosorbide-5-Nitrae-two benzene (10g, 35.9mmol) and
Carbon tetrachloride (150ml), then bromine (12.6g, 79.0mmol) is added in three times.After reaction 8 hours, saturation bisulfite is added
Sodium solution, extracted with dichloromethane, collect organic phase, concentration, crude product ethyl alcohol recrystallization, obtain 13.47g white needles crystalline substance
Body, yield：86%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, and chemistry is anti-
Answer equation as follows：
Embodiment 3：2,2 '-(hexyloxies of 2,5- bis-) -1,4- phenyl-bis- 4,4,5,5- tetramethyl -1,3,2- dioxa boron
The synthesis of alkane
The bromo- hexyloxy benzene (15g, 34.4mmol) of 2,5- bis- of 1,4- bis-, anhydrous tetrahydrochysene furan are added in 250mL three-necked flasks
Mutter 100mL.2.4M n-BuLis/hexane solution (35.8mL, 86mmol) is added dropwise when -78 DEG C under argon gas protection, at -78 DEG C
Lower stirring 2h.Then rapidly join 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- ethylenedioxies borate (19.3mL,
96.3mmol), continue to stir 1.5h at -78 DEG C.Reactant mixture is gradually increased to room temperature, stirring reaction 10h.Reaction solution is revolved
It is dry, it is extracted with ethyl acetate, the washing of the NaCl aqueous solution, anhydrous magnesium sulfate are dried, and concentrated, crude product purified by silica gel column chromatography carries
Pure, eluant, eluent is petroleum ether/dichloromethane (3:1) white solid 10.2g, yield, are obtained：56%.1H NMR、13C NMR, MS and
The compound that elementary analysis result shows to obtain is target product, and chemical equation is as follows：
Embodiment 4：The methanesulfinyl -1,1 ' of 2 ', 5 '-two hexyloxy -2 ' 2 "-two；The synthesis of 4 ' 1 "-terphenyl
Argon gas protection under, sequentially added into 250ml three-necked flask 2,2 '-(2,5- bis- hexyloxy)-Isosorbide-5-Nitrae-phenyl-
Double 4,4,5,5- tetramethyls -1,3, the bromo- 2- first iodosobenzene () of 2- dioxaborinates (9.21g, 50mmol), 1-, tetrabutyl bromine
Change ammonium (), tetra-triphenylphosphine palladium () and toluene solvant 100ml, be heated with stirring to 110 DEG C, add 50wt% wet chemicals
(24.6ml, 125mmol), react 24 hours；Solvent is spin-dried for, the purification of crude product purified by silica gel column chromatography, eluant, eluent is petroleum ether/bis-
Chloromethanes (4:1) light yellow viscous liquid 10.2g, yield, are obtained：74%.1H NMR、13C NMR, MS and elementary analysis result table
Bright obtained compound is target product, and chemical equation is as follows：
Embodiment 5：Compound M1 synthesis
At room temperature, by methanesulfinyl -1 of 2 ', 5 '-two hexyloxy -2 ' 2 "-two, 1 '；4 ' 1 "-terphenyl (8.6g,
15.5mmol) it is added in 10mL trifluoromethayl sulfonic acids, 20h is stirred under room temperature condition, reaction solution is added drop-wise in frozen water afterwards.
Reaction solution is filtered to obtain flaxen solid powder and dried afterwards.Faint yellow solid powder is added in 100mL pyridines,
6h is heated to reflux under logical condition of nitrogen gas.Stop reacting and be cooled to room temperature, extract and excess pyridine is neutralized with hydrochloric acid.With pure oil
Ether carries out column chromatography, and obtains yellow powdery solid (2.43g, 32%) with ethyl alcohol recrystallization.1H NMR、13C NMR, MS and
The compound that elementary analysis result shows to obtain is target product, and chemical equation is as follows：
Embodiment 5：Compound M2 synthesis
Compound M1 (1.80g, 3.67mmol), iodine (46mg, 0.18mmol) are added 40ml and is added in dichloromethane, is kept away
Under optical condition, bromine (1.29g, 8.07mmol) is added dropwise, reacts 10 hours；Saturation sodium hydrogensulfite water is added into reaction system
Solution, system to be treated in colourless, separate organic phase, concentration, for crude product by the Methods For Purification of column chromatography, petroleum ether is eluant, eluent,
Finally give 1.55g yellow solids, yield 65%.1H NMR、13C NMR, MS and elementary analysis result show obtained compound
It is as follows for target product, chemical equation：
Embodiment 6：Compound M3 synthesis
Compound M2 (1.2g, 1.85mmol) and 3- chloroperoxybenzoic acids (3.4g, 20mmol) are dissolved in 120mL dichloros
In methane, after stirring reaction 5h, reaction solution is poured into the sodium hydrate aqueous solution of 10% cold mass concentration and stir 30min.
Organic layer is washed with water three times, collects organic phase, concentrates and is purified by chromatographic column, eluant, eluent is dichloromethane/ethyl acetate (body
Product ratio：1:2), then yellow solid (1.12g, 85%) is obtained with ethyl alcohol recrystallization.1H NMR、13C NMR, MS and elementary analysis
As a result the compound for showing to obtain is target product, and chemical equation is as follows：
Embodiment 7：The synthesis of 4- n-octyl triphenylamines
Full liquid dissolving 4- octyl groups bromobenzene (2.69g, 10mmol) and aniline (0.93g, 23mmol) are dissolved with 150ml toluene,
Tert-butyl group sodium alkoxide (3.94g, 41mmol) and palladium (96mg, 0.5mmol) are added, under argon gas protection, oil bath is warming up to
85 DEG C, continuously add the toluene solution (1.0mol/L, 0.5mL) of tri-butyl phosphine；After reaction 12 hours, reaction solution is added water to
In reaction is quenched, with dichloromethane extraction three times, after organic phase is washed with deionized three times, dry, concentration, crude product silica gel
Column chromatography separating-purifying, pure petroleum ether obtain white solid as eluent.Yield 82%.1H NMR、13C NMR, MS and
The compound that elementary analysis result shows to obtain is target product, and chemical equation is as follows：
Embodiment 8：The synthesis of 4,4 '-two bromo- 4 "-octyl group triphenylamines
4- n-octyls triphenylamine (2.50g, 7mmol) is completely dissolved with 20ml DMFs, in 0 DEG C of condition
Under, the DMF solution of N- bromo-succinimides (NBS, 2.74g, 15.4mmol) is added dropwise, under the conditions of lucifuge
Reaction 4 hours；Reaction solution is poured into water, stirred, filtering, filter cake silica gel column chromatography separating-purifying, pure petroleum ether conduct
Eluent, obtain white solid.Yield 78%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is
Target product, chemical equation are as follows：
Embodiment 9：4,4 '-two (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-phenyl) -4 "-octyl group
The synthesis of triphenylamine
4 are completely dissolved with 100ml anhydrous tetrahydro furans (THF) solution, 4 '-two bromo- 4 "-octyl group triphenylamines (2.58g,
5mmol), under argon gas protection, -78 DEG C are cooled to, the hexane solution of 5.3ml n-BuLi is added dropwise, and (concentration is
2.4mol L-1), it is disposable to add 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- ethylenedioxy boric acid after reacting 1 hour
Ester (2.6g, 14mmol), continue stirring 2 hours；Reaction system is gradually increased to normal-temperature reaction 24 hours；Reaction solution is concentrated, according to
It is secondary to be extracted with ethyl acetate three times, after organic phase is washed with deionized three times, dry, concentration, crude product silica gel column chromatography
Separating-purifying, petrol ether/ethyl acetate (5/1, v/v) mixed solvent obtain white solid as eluent.Yield 69%.1H
NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, and chemical equation is as follows：
Embodiment 10：The synthesis of 3,6- dibromo carbazoles
Carbazole (1.67g, 10mmol) is completely dissolved with 300ml dichloromethane solutions, adds 30g 100-200 mesh silicon
Glue, under condition of ice bath (0 DEG C), N- bromo-succinimides (NBS, 3.92g, 22mmol) is added in three batches, in lucifuge condition
Lower reaction 12 hours；Reaction solution is filtered again, filter cake is washed 5 times with dichloromethane, collects organic phase, is dried, and concentration, crude product is used
Dichloromethane/petroleum ether (5/100, v/v) recrystallizes three times, obtains white solid.Yield 83%.1H NMR、13C NMR, MS and
The compound that elementary analysis result shows to obtain is target product, and chemical equation is as follows：
Embodiment 11：The synthesis of the bromo- N- iso-octyl carbazoles of 3,6- bis-
3,6- dibromos carbazole (2.28g, 7mmol) is completely dissolved with 80ml toluene solutions, adds TBAB
(0.11g, 0.35mmol), under argon gas protection, oil bath is warming up to 85 DEG C, continuously adds 50wt% sodium hydroxide (2.8g/
2.8ml deionized waters, 70mmol) aqueous solution, after stirring 1 hour, rapidly join iso-octyl bromine (2.03g, 10.5mmol)；Reaction
After 8 hours, add water in reaction solution and reaction is quenched, with dichloromethane extraction three times, organic phase is washed with deionized three times
Afterwards, dry, concentration, crude product silica gel column chromatography separating-purifying, pure petroleum ether obtains white solid as eluent.Yield
94%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, chemical equation
It is as follows：
Embodiment 12：3,6- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-N- iso-octyl carbazoles
Synthesis
The bromo- N- iso-octyl carbazoles (2.19g, 5mmol) of 3,6- bis- are completely dissolved with the anhydrous THF of 100ml, are protected in argon gas
Under, -78 DEG C are cooled to, 2.4mol L are added dropwise-1N-BuLi hexane solution (5.3ml, 12.5mmol), react 1 hour
Afterwards, disposable addition 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- ethylenedioxies borate (2.79g, 15mmol), after
Continuous stirring 2 hours.Reaction system is gradually increased to normal-temperature reaction 24 hours；Reaction solution is concentrated, three are extracted with ethyl acetate successively
It is secondary, after organic phase is washed with deionized three times, dry, concentration, crude product silica gel column chromatography separating-purifying, petroleum ether/second
Acetoacetic ester (6/1, v/v) mixed solvent obtains white solid as eluent.Yield 67%.1H NMR、13C NMR, MS and member
The compound that plain analysis result shows to obtain is target product, and chemical equation is as follows：
Embodiment 13：The synthesis of the bromo- N- iso-octyl carbazoles of 2,7- bis-
2,7- dibromos carbazole (3.25g, 10mmol) is completely dissolved with 80ml toluene, adds TBAB
(0.16g, 0.5mmol), under argon gas protection, oil bath is warming up to 85 DEG C, continuously adds 50wt% sodium hydroxide (4.0g/
4.0ml deionized waters, 0.1mol) aqueous solution, after stirring 1 hour, rapidly join iso-octyl bromine (2.32g, 12mmol)；Reaction 8
After hour, add water in reaction solution and reaction is quenched, with dichloromethane extraction three times, organic phase is washed with deionized three times
Afterwards, dry, concentration, crude product silica gel column chromatography separating-purifying, pure petroleum ether obtains white solid as eluent.Yield
94%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, chemical equation
It is as follows：
Embodiment 14：2,7- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-N- iso-octyl carbazoles
Synthesis
With 100ml anhydrous tetrahydro furans (THF) solution be completely dissolved the bromo- N- iso-octyl carbazoles of 2,7- bis- (3.5g,
8mmol), under argon gas protection, -78 DEG C are cooled to, 2.4mol L are added dropwise dropwise-1N-BuLi hexane solution
(8.4ml, 20mmol), it is disposable to add 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- ethylenedioxies after reacting 1 hour
Borate (4.17g, 22.4mmol), continue stirring 2 hours；Reaction system is gradually increased to normal-temperature reaction 24 hours；By reaction solution
Concentration, is extracted with ethyl acetate three times successively, after organic phase is washed with deionized three times, dries, concentration, crude product silicagel column
Chromatography separating-purifying, petrol ether/ethyl acetate (6/1, v/v) mixed solvent obtain white solid as eluent.Yield
67%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, chemical equation
It is as follows：
Embodiment 15：The synthesis of hexamethylene -1,4- dicarbapentaborane-two (3- bromophenyls) hydrazone
With 200ml ethanol dissolving 3- bromobenzenes hydrazine hydrochloride (11.2g, 50mmol) and sodium acetate (4.1g, 50mmol), stirring
It is well mixed；Under argon gas protection, Isosorbide-5-Nitrae-cyclohexanedione (2.81g, 25mmol) ethanol solution (100ml) is slowly added to, so
Oil bath is warming up to 60 DEG C afterwards, reacts 5 hours；After stopping reaction, reaction solution is poured into frozen water, stirred, filters separation filter cake, and
Washed with ice ethanol, obtain brown solid, yield 75%, low-temperature dark is handled after solid drying, is directly used in down without processing
Single step reaction.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, chemical reaction side
Formula is as follows：
Embodiment 16：The synthesis of the bromo indoles of 3,9- bis- [3,2-b] carbazole
With 100ml glacial acetic acid/(3- bromines of concentrated sulfuric acid mixed solution (volume ratio 4/1) dissolving hexamethylene -1,4- dicarbapentaborane-two
Phenyl) hydrazone (5.0g, 11mmol), under condition of ice bath, it is uniformly mixed；Then, oil bath is warming up to 50 DEG C, reacts 5 hours；Again
90 DEG C are warming up to, is reacted 12 hours；After stopping reaction, reaction solution is poured into frozen water, stirred, filters separation filter cake, and use ice
Ethanol washs, and obtains yellowish-brown crude product, and be recrystallized to give yellow green needle-like solid, yield 25% with DMF.1H NMR、13C
The compound that NMR, MS and elementary analysis result show to obtain is target product, and chemical equation is as follows：
Embodiment 17：The synthesis of 3,9- bis- bromo- 5,11- bis- (9- cetyls) indoles [3,2-b] carbazole
With the 40ml dimethyl sulphoxide solutions dissolving bromo indoles of 3,9- bis- [3,2-b] carbazole (2.0g, 4.8mmol), the tetrabutyl
Ammonium bromide (154mg, 0.48mmol)；Under argon gas protection, oil bath is warming up to 60 DEG C, continuously adds 50wt% sodium hydroxide
(2.7g/2.7ml deionized waters, 48mmol) aqueous solution, stirring 1 hour after, rapidly join bromohexadecane (4.4g,
14.2mmol)；After reaction 12 hours, reaction solution is poured into frozen water, stirred, filters separation filter cake, and is washed with ethanol, is obtained
Yellow solid, yield 91%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, is changed
It is as follows to learn reaction equation：
Embodiment 18：3,9- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl) (9- ten of -5,11- two
Six alkyl) indoles [3,2-b] carbazole synthesis
3,9- bis- bromo- 5,11- bis- (9- heptadecyls) indoles [3,2-b] carbazole is dissolved with 50ml dioxane solutions
(1.0g, 1.1mmol) and duplex pinacol borate (0.9g, 3.5mmol), under argon gas protection, oil bath is warming up to 80 DEG C, soon
Speed addition 1,1 '-bis- diphenylphosphine ferrocene palladium chlorides (40mg, 55 μm of ol), reacts 12 hours；After stopping reaction, it will react
Liquid concentrates, and is extracted with ethyl acetate successively three times, after organic phase is washed with deionized three times, dries, concentration, crude product silica gel
Column chromatography separating-purifying, petrol ether/ethyl acetate (5/1, v/v) mixed solvent obtain faint yellow solid as eluent.Production
Rate 56%.1H NMR、13The compound that C NMR, MS and elementary analysis result show to obtain is target product, chemical reaction equation
Formula is as follows：
It is the embodiment of polymerisation below, suitable for same type of any polymerisation.
Embodiment 19：Polymer P 1 synthesizes
Under argon gas protection, by 4,4 '-two (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-phenyl) -
4 "-octyl group triphenylamine (304.7mg, 0.50mmol) and compound M3 (356.2mg, 0.50mmol) are dissolved in 12ml toluene,
Add tetraethyl aqueous hydroxylamine solution (1.5ml, wt%=20%), palladium (1.12mg, 5 μm of ol) and tricyclohexyl phosphine
(2.8mg, 10 μm of ol)；Be heated to 80 DEG C reaction 24 hours after, add phenyl boric acid (15mg, 0.13mmol) block 6 hours, then add
Enter bromobenzene (0.25ml, 2.0mmol) to block 6 hours；Reaction stops, after cooling, by organic phase precipitating in methanol (200ml),
Filtering, after drying, crude product is successively extracted with methanol, acetone, n-hexane, dissolves polymer with toluene, using toluene as eluent,
Column chromatography purification is carried out with neutral alumina；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry
It is dry, obtain fibrous polymer.
Fig. 2 is single photon fluorescence spectrogram of the polymer P 1 in opposed polarity solvent, and solvent is respectively the first of low pole
Benzene, tetrahydrofuran, the dichloromethane of middle polarity, highly polar DMF.Polymer is in different solvents
Maximum single photon fluorescence intensity weakens as solvent polarity increases, and maximum fluorescence intensity is 1.58 × 10 in toluene solvant7；
Emission maximum peak value is from 525nm (toluene solvant) red shifts to 572nm (DMF solvent), Intramolecular electron transfer
Substantially.This is all advantageous to the enhancing of the ability of two-photon absorption.
Embodiment 20：Polymer P it is 2-in-1 into
Under argon gas protection, by 3,6- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-N- iso-octyl
Carbazole (265.7mg, 0.50mmol) and compound M3 (356.2mg, 0.50mmol) are dissolved in 12ml toluene, add tetrem
Base aqueous hydroxylamine solution (1.5ml, wt%=20%), palladium (1.12mg, 5 μm of ol) and tricyclohexyl phosphine (2.8mg, 10 μ
mol)；Be heated to 80 DEG C reaction 24 hours after, add phenyl boric acid (15mg, 0.13mmol) block 6 hours, add bromobenzene
(0.25ml, 2.0mmol) is blocked 6 hours；Reaction stops, and after cooling, by organic phase precipitating in methanol (200ml), filters, does
After dry, crude product is successively extracted with methanol, acetone, n-hexane, polymer is dissolved with toluene, using toluene as eluent, with neutrality
Aluminum oxide carries out column chromatography purification；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains
Fibrous polymer.
Fig. 3 is two-photon fluorescence spectrogram of the polymer P 2 in toluene solution under different optical maser wavelengths；It can be seen that
Optical maser wavelength from 720nm progressively increase to 940nm when, the two-photon fluorescence intensity of polymer P 2 is 103More than, work as optical maser wavelength
For 760nm when, the two-photon fluorescence intensity of polymer is up to 1.97 × 105, higher fluorescence intensity illustrates that polymer has
Stronger two-photon response.
Embodiment 21：Polymer P 3 synthesizes
Under argon gas protection, by 2,7- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-N- iso-octyl
Carbazole (265.7mg, 0.50mmol) and compound M3 (356.2mg, 0.50mmol) are dissolved in 12ml toluene, add tetrem
Base aqueous hydroxylamine solution (1.5ml, wt%=20%), palladium (1.12mg, 5 μm of ol) and tricyclohexyl phosphine (2.8mg, 10 μ
mol)；Be heated to 80 DEG C reaction 24 hours after, add phenyl boric acid (15mg, 0.13mmol) block 6 hours, add bromobenzene
(0.25ml, 2.0mmol) is blocked 6 hours；Reaction stops, and after cooling, by organic phase precipitating in methanol (200ml), filters, does
After dry, crude product is successively extracted with methanol, acetone, n-hexane, polymer is dissolved with toluene, using toluene as eluent, with neutrality
Aluminum oxide carries out column chromatography purification；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains
Fibrous polymer.
Embodiment 22：Polymer P 4 synthesizes
Under argon gas protection, by 3,9- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl) -5,11- bis-
(9- cetyls) indoles [3,2-b] carbazole (478.6mg, 0.50mmol) and compound M3 (356.2mg, 0.50mmol) dissolvings
In 12ml toluene, add tetraethyl aqueous hydroxylamine solution (1.5ml, wt%=20%), palladium (1.12mg, 5 μm of ol) and
Tricyclohexyl phosphine (2.8mg, 10 μm of ol)；Be heated to 80 DEG C reaction 24 hours after, add phenyl boric acid (15mg, 0.13mmol) end-blocking
6 hours, add bromobenzene (0.25ml, 2.0mmol) and block 6 hours；Reaction stops, after cooling, by organic phase precipitating in methanol
In (200ml), filtering, after drying, crude product is successively extracted with methanol, acetone, n-hexane, polymer is dissolved with toluene, with first
Benzene is eluent, and column chromatography purification is carried out with neutral alumina；The toluene solution of concentrated polymer, precipitating is in methanol solution again
In, filter, dry, obtain fibrous polymer
Embodiment 23：The two-photon absorption performance test to receptor type alternating polymer of the condensed cyclic structure containing sulfuryl
By two-photon fluorescence revulsion receptor type alternating polymer is given to the condensed cyclic structure of the present invention containing sulfuryl
Two-photon absorption performance tested；Ti∶sapphire laser femto-second laser (Avesta TiF-100M) conduct is used during experiment test
Pump light source, the pulse width of laser are 80fs, frequency 84.5Hz, and laser excitation energy is 100mw, the thang-kng length of pulse
For 10mm quartz sample pool.Polymer P 1 is dissolved in the solvent of four kinds of opposed polarities, respectively toluene, tetrahydrofuran, two
Chloromethanes, N,N-dimethylformamide；2~P4 of polymer P is dissolved in toluene solution, and the concentration of all solution is 1 × 10- 6mol L-1.Standard specimen is the 0.1mol L of fluorescein-1Sodium hydrate aqueous solution, concentration be 1 × 10-6mol L-1, its fluorescence volume
Sub- yield is 88%.Polymer P 1-P4 is as shown in table 1 in the fluorescence quantum yield test result of solution state.
1~the P4 of polymer P of table 1 fluorescence quantum yield
As known from Table 1, the fluorescence quantum yield of polymer P 1 is 73% under toluene solution state, as solvent polarity increases
DMF is added to, fluorescent quantum quantum yield drops to 5%.This explanation polymer P 1 is in low pole toluene solution
In there are stronger two-photon response potentiality.The polarity for also demonstrating that solvent simultaneously is to influence a weight of polymer two-photon response
Want factor.1~P4 of polymer P fluorescence quantum yield is respectively 73%, 51%, 65% and 67% in toluene solution, compared with
High fluorescence quantum yield illustrates that polymer has huge application prospect in the application field of two-photon absorption.
The two photon absorption cross section of compound can be calculated according to the fluorescence quantum yield of polymer and two-photon fluorescence spectrum
δ, calculation formula are as follows：
In above-mentioned formula, 1 represents standard specimen, the 0.1mol L of fluorescein-1Sodium hydrate aqueous solution；2 represent testing sample.
I1、I2Represent standard specimen, testing sample two-photon fluorescence spectrum integral area, two-photon fluorescence spectrogram is shown in 2,3.φ1、φ2
Represent standard specimen, the fluorescence quantum efficiency of testing sample.C1、C2Represent standard specimen, the solution concentration of testing sample.
Two photon absorption cross section of the polymer P 1 in different solvents and the graph of a relation between optical maser wavelength as shown in figure 4, from
It can be seen from the figure that, under opposed polarity solvent state, the two photon absorption cross section of polymer P 1 and the change of optical maser wavelength become
Gesture is consistent.When optical maser wavelength is 760nm and 800nm, the two photon absorption cross section value of polymer P 1 is larger.It is wherein molten in toluene
It is maximum in agent, it is 3657GM (1GM=10-50cm-4sphoton-1), now optical maser wavelength is 760nm；
When optical maser wavelength is 800nm, two photon absorption cross section value of the polymer P 1 in tetrahydrofuran solvent is up to
348GM；
When optical maser wavelength is 780nm, two photon absorption cross section of the polymer P 1 in DMF solvent
Value is up to 108GM；
Understand the polarity of solvent to material from two photon absorption cross section data of the polymer P 1 in opposed polarity solvent
Two-photon absorption performance has important influence.Suitable solvent is selected, the performance for being advantageous to the two-photon absorption of material shows.
Two photon absorption cross sections of the 2~P4 of polymer P in toluene solvant and such as Fig. 5 of the graph of a relation between optical maser wavelength institutes
Show, it can be seen that when optical maser wavelength is 780nm, the two photon absorption cross section value of polymer P 2 is up to 1308GM；
When optical maser wavelength is 720nm, the two photon absorption cross section value of polymer P 3 is up to 1005GM；
When optical maser wavelength is 780nm, the two photon absorption cross section value of polymer P 4 is up to 784GM；
1~P4 of polymer P has larger two photon absorption cross section value in whole test scope, illustrates condensed ring containing sulfuryl
Structure has good two-photon response to receptor type alternating polymer, there is actual application value.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of condensed cyclic structure containing sulfuryl gives receptor type alternating polymer with strong two-photon effect, it is characterised in that its
Shown in structural formula such as formula (1)：
In formula, A is short of electricity subelement, and D is electron rich unit.
2. the condensed cyclic structure according to claim 1 containing sulfuryl gives receptor type alternating polymerization with strong two-photon effect
Thing, it is characterised in that described short of electricity subelement A structure is any one in following structure：
In above-mentioned short of electricity subelement A structural formulas, R is selected from H, C1~C30Straight chain or branched alkyl,AndR3Selected from H, C1~C30Straight chain or branched alkyl and C1~C30Alkoxy.
3. the condensed cyclic structure according to claim 1 containing sulfuryl gives receptor type alternating polymerization with strong two-photon effect
Thing, it is characterised in that the electron rich cells D is any one in following structural formula：
In the structural formula of above-mentioned electron rich cells D, R is selected from H, C1~C30Straight chain or branched alkyl,AndR3Selected from H, C1~C30Straight chain or branched alkyl and C1~C30Alkoxy；R1、R2、R4~R7Can
It is identical or different be independently selected from H, C1~C30Straight chain or branched alkyl, C1~C30Alkoxy,AndR8Selected from H, C1~C30Straight chain or branched alkyl and C1~C30Alkoxy.
4. the condensed cyclic structure containing sulfuryl described in claim 1 or 2 or 3 there is strong two-photon effect give receptor type alternating polymerization
The preparation method of thing, it is characterised in that by Suzuki polymerize to obtain by the A of condensed cyclic structure containing sulfuryl and electron rich cells D described
The condensed cyclic structure containing sulfuryl gives receptor type alternating polymer with strong two-photon effect.
5. the condensed cyclic structure according to claim 4 containing sulfuryl gives receptor type alternating polymer with strong two-photon effect
Preparation method, it is characterised in that the preparation method comprises the following steps：
(1) under inert gas atmosphere, sulfuryl condensed cyclic structure monomer A, electron rich cells D are dissolved with toluene, add palladium and three
Cyclohexyl phosphorus and the tetraethyl ammonium hydroxide aqueous solution, heating stirring, temperature are reacted 24~36 hours at 60~110 DEG C；
(2) phenyl boric acid end-blocking is added, continues reaction 6~12 hours；Bromobenzene end-blocking is added, continues reaction 6~12 hours；
(3) after polymerization terminates, reaction solution precipitating in methyl alcohol, filtering, extracted successively with methanol, acetone and n-hexane, then with first
Benzene is eluent, and silicagel column carries out column chromatography, concentration, and precipitating in methanol solution, filters again, dries, and obtains described contain
Sulfuryl condensed cyclic structure gives receptor type alternating polymer with strong two-photon effect.
6. the condensed cyclic structure according to claim 5 containing sulfuryl gives receptor type alternating polymer with strong two-photon effect
Preparation method, it is characterised in that inert gas includes argon gas described in step (1)；
The mol ratio of short of electricity subelement A described in step (1) and electron cells D is 1:1；
The mol ratio of palladium, thricyclohexyl phosphorus and short of electricity subelement A described in step (1) is 1：2：100~150；
The volume ratio of the tetraethyl ammonium hydroxide aqueous solution and toluene described in step (1) is 1:6~10.
7. the condensed cyclic structure according to claim 5 containing sulfuryl gives receptor type alternating polymer with strong two-photon effect
Preparation method, it is characterised in that the phenyl boric acid described in step (2)：Bromobenzene：The mol ratio of short of electricity subelement be 0.2~
0.5：2~5：1.
8. the condensed cyclic structure containing sulfuryl described in claim 1 or 2 or 3 there is strong two-photon effect give receptor type alternating polymerization
Application of the thing in non-linear optical field.
9. application according to claim 8, it is characterised in that it is micro- that the non-linear optical field includes two-photon fluorescence
Technology, two-photon up-conversion lasing, optical Limiting, double photon three dimension processing, double photon three dimension optical storage and double-photon optical power
Learn treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710992465.3A CN107759775B (en) | 2017-10-23 | 2017-10-23 | Donor-receptor type alternating polymer containing sulfone-based fused ring structure and having strong two-photon effect, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710992465.3A CN107759775B (en) | 2017-10-23 | 2017-10-23 | Donor-receptor type alternating polymer containing sulfone-based fused ring structure and having strong two-photon effect, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107759775A true CN107759775A (en) | 2018-03-06 |
| CN107759775B CN107759775B (en) | 2020-06-05 |
Family
ID=61269193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710992465.3A Active CN107759775B (en) | 2017-10-23 | 2017-10-23 | Donor-receptor type alternating polymer containing sulfone-based fused ring structure and having strong two-photon effect, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107759775B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493564A (en) * | 2020-04-07 | 2021-10-12 | 中国科学院长春应用化学研究所 | Organic polymer luminescent material with D-sigma-A structure and preparation method and application thereof |
| CN116003796A (en) * | 2023-03-23 | 2023-04-25 | 东营华联石油化工厂有限公司 | Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228250A (en) * | 2005-05-20 | 2008-07-23 | 默克专利有限公司 | Compounds for organic electronic devices |
| CN106008582A (en) * | 2016-07-27 | 2016-10-12 | 东莞理工学院 | Fluorene and carbazole bridging-based A-D-A type double-center BODIPY (boron-dipyrrolemethene) derivative and preparation method for same |
| CN106243329A (en) * | 2016-07-29 | 2016-12-21 | 华南理工大学 | One is based on S, S dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and preparation method and application to receptor type |
-
2017
- 2017-10-23 CN CN201710992465.3A patent/CN107759775B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228250A (en) * | 2005-05-20 | 2008-07-23 | 默克专利有限公司 | Compounds for organic electronic devices |
| CN106008582A (en) * | 2016-07-27 | 2016-10-12 | 东莞理工学院 | Fluorene and carbazole bridging-based A-D-A type double-center BODIPY (boron-dipyrrolemethene) derivative and preparation method for same |
| CN106243329A (en) * | 2016-07-29 | 2016-12-21 | 华南理工大学 | One is based on S, S dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and preparation method and application to receptor type |
Non-Patent Citations (1)
| Title |
|---|
| PIK KWAN LO，ET AL: ""Synthesis and Structure-Linear and Structure-Nonlinear Optical Properties of Multi-Dipolar Zigzag Oligoaryleneethynylenes"", 《J. ORG. CHEM.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493564A (en) * | 2020-04-07 | 2021-10-12 | 中国科学院长春应用化学研究所 | Organic polymer luminescent material with D-sigma-A structure and preparation method and application thereof |
| CN116003796A (en) * | 2023-03-23 | 2023-04-25 | 东营华联石油化工厂有限公司 | Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination |
| CN116003796B (en) * | 2023-03-23 | 2023-07-28 | 东营华联石油化工厂有限公司 | Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107759775B (en) | 2020-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107011469B (en) | A kind of side chain type liquid crystal macromolecule and preparation method thereof with aggregation-induced emission performance | |
| CN108707221B (en) | Conjugated polymer based on naphthoindene fluorene high two-photon absorption and preparation method and application thereof | |
| Feng et al. | Naphthalene-based fluorophores: Synthesis characterization, and photophysical properties | |
| CN103172650A (en) | Strong fluorescence fluoro-boron dipyrrole compound containing triphenylamine structure as well as preparation method and application thereof | |
| CN102875750B (en) | Preparation method of polymer-rare earth ion luminous micelles | |
| CN107540823A (en) | One kind is based on S, the strong two-photon absorption conjugated polymer of S dioxydibenze bithiophene units and preparation method and application | |
| CN105669734B (en) | A kind of pyrroles fluorescence molecule BCPA BODIPY of carbazyl triphenylamine fluorine boron two and its preparation method and application | |
| Tan et al. | Carbazole-based highly solid-state emissive fluorene derivatives with various mechanochromic fluorescence characteristics | |
| CN107759775A (en) | The condensed cyclic structure containing sulfuryl gives receptor type alternating polymer, preparation method and application with strong two-photon effect | |
| CN110183475A (en) | Double boron oxa- pyrene compounds and its application based on donor-receiver | |
| CN102617855B (en) | Cyclic polymer and preparation method thereof | |
| CN105348308B (en) | Bridged bis-boron-dipyrromethene (BODIPY) derivative containing fluorene at meso-position and preparation method thereof | |
| CN110668997B (en) | Organelle targeted aggregation-induced emission material and preparation method thereof | |
| CN105111414A (en) | Conjugated polymer containing fluorene as well as preparation method and application thereof | |
| CN110527069A (en) | A kind of electroluminescent polymer and the preparation method and application thereof | |
| CN106632438B (en) | A kind of A- π-D- π-A type BODIPY derivatives and preparation method thereof based on acetenyl bridging | |
| CN102295743A (en) | Fluorescent conjugated polymer containing polyhedral oligomeric silsesquioxane (POSS), its preparation method and application | |
| CN113773338A (en) | Boron-containing organic free radical compound and preparation method and application thereof | |
| CN102863559B (en) | Photoinitiator for UV (ultraviolet)-LED curing | |
| CN104861106A (en) | Up-conversion luminescence polymer material based on triplet state-triplet annihilation | |
| CN106188505B (en) | A kind of modified polycarbazole and preparation method thereof | |
| CN104628753B (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
| CN114874145A (en) | Water-soluble trityl free-based material and preparation method and application thereof | |
| CN115650951A (en) | Diaryl ethylene organic photochromic material and preparation method thereof | |
| CN114230581A (en) | Multidentate organic ligand, preparation method and application thereof, metal supramolecular polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210629 Address after: 523808 room 236, building 15, No.1 Xuefu Road, Songshanhu Park, Dongguan City, Guangdong Province Patentee after: Dongguan Hua Gong Cooperative Innovation Technology Development Co.,Ltd. Patentee after: Huang Fei Patentee after: Ying Lei Address before: 523808 room 168, productivity building, Songshan Lake high tech Industrial Development Zone, Dongguan, Guangdong Patentee before: SOUTH CHINA INSTITUTE OF COLLABORATIVE INNOVATION |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210816 Address after: 523808 room 533, building 15, No.1 Xuefu Road, Songshanhu Park, Dongguan City, Guangdong Province Patentee after: Dongguan volt ampere Photoelectric Technology Co., Ltd Address before: 523808 room 236, building 15, No.1 Xuefu Road, Songshanhu Park, Dongguan City, Guangdong Province Patentee before: Dongguan Hua Gong Cooperative Innovation Technology Development Co.,Ltd. Patentee before: Huang Fei Patentee before: Ying Lei |