CN108707221A - Conjugated polymer and the preparation method and application thereof of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes - Google Patents

Conjugated polymer and the preparation method and application thereof of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes Download PDF

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CN108707221A
CN108707221A CN201810406637.9A CN201810406637A CN108707221A CN 108707221 A CN108707221 A CN 108707221A CN 201810406637 A CN201810406637 A CN 201810406637A CN 108707221 A CN108707221 A CN 108707221A
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naphtho
photon
reaction
polymer
photon absorption
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CN108707221B (en
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应磊
郭婷
胡黎文
彭俊彪
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South China University of Technology SCUT
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Abstract

The invention discloses conjugated polymer and the preparation method and application thereof of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes.The present invention is using naphtho- indenes fluorenes unit as core, and by MOLECULE DESIGN and the reasonable selection of group, a kind of conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes is made by Suzuki polymerisations.The conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes of the present invention has strong single photon fluorescence and two-photon fluorescence intensity, there is good dissolubility simultaneously, it can be dissolved in common organic solvent, convenient for the test and application of two-photon absorption performance, in nonlinear optics and biological imaging field tool actual application value.

Description

Conjugated polymer and preparation method thereof of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes With application
Technical field
The present invention relates to two-photon fluorescence polymer arts, and in particular to one kind is based on the high two-photon absorption of naphtho- indenes fluorenes Conjugated polymer and the preparation method and application thereof.
Background technology
Took the lead in proposing the concept of two-photon absorption in Goppert-Mayer in 1931, and theoretically calculates double light The transition probability of subprocess.Material (is indicated, V under the action of strong light (such as laser) by intermediate virtual stake with V1, V2Can wait can not Absorb equally) and simultaneously energy (the hv of two photons1+hv2) after, from ground state S0Transit to excitation state Sn(SnEnergy level is two photons Energy) process be known as two-photon absorption (TPA).Between the limitation of experiment condition, until the appearance of laser at the beginning of the sixties, Kaiser just in an experiment first observed to this phenomenon, it was confirmed that the prophesy of Goppert-Mayer.Two-photon absorption is a kind of Nonlinear optical phenomena, with the rapid advances of laser technology, researchers are more and more deep to probing into for two-photon absorption, it In addition to being a kind of spectral results, it is broadly extended to three-dimensional information storage, two-photon up-conversion lasing, two-photon absorption The fields such as optical Limiting, two-photon fluorescence microscope, photodynamic therapy.
Most important with strong two-photon absorbing material is characterized in that in molecular structure with larger conjugated system. Naphtho- indenes fluorenes unit is the high unit of rigid planar structure, a fluorescence quantum yield, and naphtho- indenes fluorenes unit is introduced polymer In main chain, there is higher fluorescence quantum yield and excellent dissolubility, be conducive to the two-photon absorption ability for enhancing polymer.
Invention content
The purpose of the present invention is to provide conjugated polymer of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes.The polymer Feature with the response of preferable dissolubility, higher fluorescence quantum yield and strong two-photon.
The present invention also aims to provide a kind of conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes Preparation method.This method is made with big conjugate planes naphtho- indenes fluorenes unit and different units by Suzuki polycondensation reactions A kind of conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes.
The present invention also aims to provide a kind of conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes Application.
The purpose of the present invention is achieved through the following technical solutions.
Conjugated polymer of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes, the polymer formulae are as follows：
In formula, n=1~1000；R is C1~C30Straight chain or branched alkyl or be C1~C30Alkoxy or be benzene Oxygroup.
Preferably, the Ar is any one in following structural formula：
Wherein, R1~R6Can be identical or different, it is independently selected from H, C1~C30Straight chain or branched alkyl or be C1~ C30Alkoxy or be phenoxy group.
The preparation method of above-described conjugated polymer of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes, including it is as follows Step：
(1) under inert gas protection, the monomer of naphtho- indenes fluorenes unit and the structure containing Ar is completely dissolved with organic solvent, Under catalyst action and tetraethyl ammonium hydroxide effect, 60~100 DEG C of generation Suzuki polymerisations are heated to, the reaction time is 12~36h；
(2) it is added phenyl boric acid into reaction solution obtained by step (1), 60~100 DEG C of constant temperature the reaction was continued 6~12h；It adds 60~100 DEG C of continuation 6~12h of isothermal reaction of bromobenzene, reaction purify gained reaction solution to get high based on naphtho- indenes fluorenes after stopping The conjugated polymer of two-photon absorption.
Preferably, step (1) described inert gas is argon gas；The organic solvent be toluene, tetrahydrofuran, dimethylbenzene, At least one of dioxane and N,N-dimethylformamide.
Preferably, the catalyst is the combination in palladium source and phosphine source；The palladium source is palladium and three (dibenzylidenes third Ketone) one kind in two palladiums；The phosphine source is at least one in thricyclohexyl phosphorus, tetra-triphenylphosphine palladium and triphenylphosphine palladium Kind.
Preferably, the naphtho- indenes fluorenes unit described in step (1), the structure containing Ar the dosage of monomer meet containing double borate officials It can group or the monomer integral molar quantity containing double boric acid functional groups and the monomer integral molar quantity containing double bromo functional groups or the functional group containing Shuan Dian It is equal.
Preferably, the dosage of step (1) described catalyst is 5 ‰~the 3% of reaction monomers moles total number；The reaction is single Body includes naphtho- indenes fluorenes unit and the monomer (similarly hereinafter) of the structure containing Ar.
Preferably, the dosage of the phenyl boric acid described in step (2) is the 10~20%. of reaction monomers moles total number
Preferably, the dosage of the bromobenzene described in step (2) is 2~5 times of phenyl boric acid mole.
Preferably, the purifying described in step (2) refers to being cooled to room temperature gained reaction solution, pours into methanol and precipitates, mistake Filter, dry that crude product, crude product are successively extracted with methanol, acetone, n-hexane, again with toluene dissolving, column chromatography for separation, concentration Precipitating is in methanol solution again afterwards, filtering, dry to get target product.
Above-described conjugated polymer of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes is micro-, double in two-photon fluorescence Photon up-conversion lasing, optical Limiting, double photon three dimension processing, double photon three dimension optical storage, double-photon optical photodynamic therapy etc. In application.
Preferably, in application process, the strong and weak use of the two-photon absorption performance of the conjugated polymer based on naphtho- indenes fluorenes is double Photon absorption cross sections are weighed, and two photon absorption cross section value is bigger, the two-photon absorption ability of polymer is stronger, and response is faster.
Preferably, the test mode of the two photon absorption cross section is：By the conjugated polymers based on naphtho- indenes fluorenes Object is dissolved with organic solvent, then passes through two-photoninduced fluorescence method, Z- scanning techniques, nonlinear transmission method or two-photon transient state Absorption spectrometry is tested.
Preferably, the organic solvent includes toluene, dimethylbenzene, n-hexane, ether, dioxane, dichloromethane, trichlorine Methane, ethyl acetate, tetrahydrofuran, 1,2- dichloroethanes, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, two Methyl sulfoxide or chlorobenzene.
Compared with prior art, the present invention has the advantage that and advantageous effect：
(1) conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes of the invention, due to being grown with larger conjugation Degree is conducive to the two-photon absorption ability for enhancing polymer so there is higher fluorescence quantum yield.
(2) conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes of the invention has strong single photon fluorescence and double Photon fluorescence intensity, while there is good dissolubility, it can be dissolved in common organic solvent, convenient for two-photon absorption performance Test and application, in nonlinear optics and biological imaging field tool actual application value.
(3) the present invention is based in the conjugated polymer preparation process of the high two-photon absorption of naphtho- indenes fluorenes, raw material is cheap, cost It is low；Simultaneously synthesizing step is easy, and yield is high, is conducive to scale of mass production.
Description of the drawings
Fig. 1 is single photon fluorescence spectrogram of the polymer P 1 in opposed polarity solvent；
Fig. 2 is the two-photon fluorescence spectrogram of the polymer P 2 under different optical maser wavelengths；
Fig. 3 is that the relationship of polymer P 1 optical maser wavelength and two photon absorption cross section value in toluene and dichloromethane solvent is bent Line chart.
Specific implementation mode
Below in conjunction with specific embodiment and attached drawing, technical scheme of the present invention is further explained, but the present invention does not limit to In this.
The synthesis of 1 polymer P 1 of embodiment
(1) synthesis of 4- n-octyls triphenylamine：
It is completely dissolved 4- octyls bromobenzene (2.69g, 10mmol) and aniline (0.93g, 23mmol) with 150ml toluene solvants, Tertiary butyl sodium alkoxide (3.94g, 41mmol) and palladium (96mg, 0.5mmol) are added, under protection of argon gas, oil bath is warming up to 85 DEG C, continuously add the toluene solution (2.0mol/L, 0.5mL) of tri-tert-butylphosphine；After reaction 12 hours, reaction solution is added water to In reaction is quenched, three times with dichloromethane extraction, dry after organic phase is washed with deionized three times, 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 result shows that obtained compound is target product, chemical equation is as follows for elemental analysis：
The synthesis of (2) 4,4 '-two bromo- 4 "-octyl triphenylamines：
It is completely dissolved 4- n-octyls triphenylamine (2.50g, 7.0mmol) with 20ml n,N-Dimethylformamide, in 0 DEG C of item Under part, n,N-Dimethylformamide (DMF) solution of N- bromo-succinimides (NBS, 2.74g, 15.4mmol) is added dropwise, is protected from light Under the conditions of react 4 hours；Reaction solution is poured into water, is stirred, filtering, filter cake silica gel column chromatography separating-purifying, pure oil Ether obtains white solid as eluent.Yield 78%.1H NMR、13C NMR, MS and elemental analysis are the result shows that obtained change Conjunction object is target product, and chemical equation is as follows：
(3) 4,4 '-two (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-phenyl) -4 "-octyl triphen The synthesis of amine：
4,4 '-two bromo- 4 "-octyl triphenylamines (2.58g, 5mmol) are completely dissolved with 100ml anhydrous tetrahydro furans (THF), Under protection of argon gas, -78 DEG C are cooled to, hexane solution (a concentration of 2.4mol L of the n-BuLi of 5.3ml are added dropwise-1), After reaction 1 hour, it is added at one time 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- ethylenedioxies borate (2.6g, 14mmol), continue stirring 2 hours；Reaction system is gradually increased to normal-temperature reaction 24 hours；Reaction solution is concentrated, uses acetic acid successively Ethyl ester extracts three times, dry after organic phase is washed with deionized three times, concentration, crude product silica gel column chromatography separating-purifying, Petrol ether/ethyl acetate (5/1, v/v) mixed solvent obtains white solid as eluent.Yield 69%.1H NMR、13C The result shows that obtained compound is target product, chemical equation is as follows for NMR, MS and elemental analysis：
(4) polymer P 1 synthesizes：
Under argon gas protection, by 4,4 '-two (4,4 ', 5,5 '-tetramethyls -1,3,2- dioxaborinates-diyl)-phenyl) - Tetra- n-hexyl -7,13- dihydrobenzos of 4 "-octyl triphenylamines (304.7mg, 0.50mmol) and bis- bromo- 7,7,13,13- of 5,10- [g]Yin [1,2-b]Fluorenes (455.5mg, 0.50mmol) is dissolved in 12ml toluene, adds palladium (3.93mg, 17.5 μ Mol) and tricyclohexyl phosphine (9.81mg, 35.0 μm of ol), 3mL tetraethyl ammonium hydroxides are then added, are warming up to 80 DEG C, reaction 24 Hour；Then 18.3mg (0.15mmol) phenyl boric acid is added to be blocked, after 12 hours, then with 47.1mg (0.30mmol) bromobenzene It is blocked；After the reaction was continued 12 hours, stop reaction, wait for that temperature is down to room temperature, product is added dropwise and is sunk in 300mL methanol Analysis, filtering, then crude product is dissolved in the toluene of 20mL, using 200~300 mesh silica gel as stationary phase, with toluene be eluant, eluent into Row column chromatography, solvent concentration separate out come again in methyl alcohol, stir, and filtering obtains polymer solids after vacuum drying；Most It is respectively extracted 24 hours with methanol, acetone, tetrahydrofuran successively again afterwards, removes small molecule；By the tetrahydrofuran solution drop after concentration Enter precipitating in methanol, the fibrous solids polymer P 1 obtained after vacuum drying.1H NMR, GPC and elemental analysis the result shows that Obtained polymer is target product, and preparation process chemical equation is as follows：
Single photon fluorescence spectrogram of the polymer P 1 in opposed polarity solvent is shown in Fig. 1.As can be known from Fig. 1, solvent polarity Highly polar DMF is changed to by low pole toluene, the gradual red shift of spectrum of polymer P 1 illustrates that intramolecular turns with stronger charge It moves, and the fluorescence intensity of polymer is stronger, in toluene solvant, fluorescence intensity is 1.84 × 107；In DMF solvent, fluorescence is strong Degree is 3.89 × 106.Strong fluorescence intensity means the potentiality that polymer P 1 has strong two-photon to respond.
The synthesis of 2 polymer P 2 of embodiment
(1) synthesis of 3,6- dibromos carbazole：
It is completely dissolved carbazole (1.67g, 10mmol) with 300ml dichloromethane, adds the 100-200 mesh silica gel of 30g, Under condition of ice bath (0 DEG C), N- bromo-succinimides (NBS, 3.92g, 22mmol) are added in three batches, are reacted under the conditions of being protected from light 12 hours；Reaction solution is filtered again, filter cake is washed 5 times with dichloromethane, collects organic phase, dry, concentration, crude product dichloromethane Alkane/petroleum ether (5/100, v/v) recrystallizes three times, obtains white solid.Yield 83%.1H NMR、13C NMR, MS and element point The result shows that obtained compound is target product, chemical equation is as follows for analysis：
(2) synthesis of bis- bromo- N- iso-octyl carbazoles of 3,6-：
Be completely dissolved 3,6- dibromos carbazole (2.28g, 7mmol) with 80ml toluene, add tetrabutylammonium bromide (0.11g, 0.35mmol), under protection of argon gas, oil bath is warming up to 85 DEG C, continuously add 50wt% sodium hydroxide (2.8g/2.8ml go from Sub- water, 70mmol) aqueous solution, after stirring 1 hour, iso-octyl bromine (2.03g, 10.5mmol) is added；After reaction 8 hours, by water It is added in reaction solution and reaction is quenched, three times with dichloromethane extraction, dry after organic phase is washed with deionized three times, concentration, Crude product silica gel column chromatography separating-purifying, pure petroleum ether obtain white solid as eluent.Yield 94%.1H NMR、13C The result shows that obtained compound is target product, chemical equation is as follows for NMR, MS and elemental analysis：
(3) synthesis of 3,6- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-N- iso-octyl carbazoles：
3,6-, bis- bromo- N- iso-octyl carbazoles (2.19g, 5mmol) 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, it is added at one time 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, dry after organic phase is washed with deionized three times, 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 is target product, and chemical equation is as follows：
(4) polymer P 2 synthesizes：
Under argon gas protection, by 3,6- bis- (4,4 ', 5,5 '-tetramethyls -1,3,2- dioxaborinates-diyl)-N- iso-octyl Tetra- n-hexyl -7,13- dihydrobenzos of carbazole (265.7mg, 0.50mmol) and bis- bromo- 7,7,13,13- of 5,10-;g]Yin [1,2- b]Fluorenes (455.5mg, 0.50mmol) is dissolved in 12ml toluene, adds palladium (3.93mg, 17.5 μm of ol) and three hexamethylenes 3mL tetraethyl ammonium hydroxides are then added in base phosphine (9.81mg, 35.0 μm of ol), are warming up to 80 DEG C, react 24 hours；Then plus Enter 18.3mg (0.15mmol) phenyl boric acid to be blocked, after 12 hours, then be blocked with 47.1mg (0.30mmol) bromobenzene；After After continuing reaction 12 hours, stop reaction, wait for that temperature is down to room temperature, the precipitating in 300mL methanol is added dropwise in product, is filtered, then Crude product is dissolved in the toluene of 20mL, is that eluant, eluent carries out column chromatography with toluene using 200~300 mesh silica gel as stationary phase, it is molten Agent concentrates, and separates out come in methyl alcohol again, stirs, and filtering obtains polymer solids after vacuum drying；Finally use first successively again Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, The fibrous solids polymer P 2 obtained after vacuum drying.1H NMR, GPC and elemental analysis are the result shows that obtained polymer For target product, preparation process chemical equation is as follows：
Two-photon fluorescence spectrogram of the polymer P 2 in toluene solvant is shown in Fig. 2.As can be known from Fig. 2, the fluorescence of polymer The peak value of spectrum is 488nm, is the transmitting of polymer conjugated main chain.Change the wavelength of laser, the two-photon fluorescence of polymer P 2 Intensity first increases afterwards to reduce to be reduced again in increase.When optical maser wavelength is 730nm, the two-photon fluorescence intensity of polymer is most strong, It is 3.98 × 106.This means that under this wavelength, the two photon absorption cross section value of polymer P 2 is maximum.
The synthesis of 3 polymer P 3 of embodiment
(1) synthesis of bis- bromo- N- iso-octyl carbazoles of 2,7-：
It is completely dissolved 2,7- dibromos carbazole (3.25g, 10mmol) with 80ml toluene, adds tetrabutylammonium bromide (0.16g, 0.5mmol), under protection of argon gas, oil bath are warming up to 85 DEG C, continuously add the sodium hydroxide (4.0g/ of 50wt% 4.0ml deionized waters, 0.1mol) aqueous solution, after stirring 1 hour, iso-octyl bromine (2.32g, 12mmol) is added；Reaction 8 hours Afterwards, it adds water in reaction solution and reaction is quenched, three times with dichloromethane extraction, after organic phase is washed with deionized three times, do Dry, concentration, crude product silica gel column chromatography separating-purifying, pure petroleum ether obtains white solid as eluent.Yield 94%.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, the following institute of chemical equation Show：
(2) synthesis of 2,7- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-N- iso-octyl carbazoles：
2,7-, bis- bromo- N- iso-octyl carbazoles (3.5g, 8mmol) are completely dissolved with 100ml anhydrous tetrahydro furans (THF), Under argon gas protection, -78 DEG C are cooled to, 2.4mol L are added dropwise dropwise-1N-BuLi hexane solution (8.4ml, 20mmol), After reaction 1 hour, it is added at one time 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- ethylenedioxies borate (4.17g, 22.4mmol), continue stirring 2 hours；Reaction system is gradually increased to normal-temperature reaction 24 hours；Reaction solution is concentrated, uses second successively Acetoacetic ester extracts three times, dry after organic phase is washed with deionized three times, and concentration, crude product silica gel column chromatography separation carries Pure, petrol ether/ethyl acetate (6/1, v/v) mixed solvent obtains white solid as eluent.Yield 67%.1H NMR、13C The result shows that obtained compound is target product, chemical equation is as follows for NMR, MS and elemental analysis：
(3) polymer P 3 synthesizes：
Under argon gas protection, by 2,7- bis- (4,4 ', 5,5 '-tetramethyls -1,3,2- dioxaborinates-diyl)-N- iso-octyl Tetra- n-hexyl -7,13- dihydrobenzos of carbazole (265.7mg, 0.50mmol) and bis- bromo- 7,7,13,13- of 5,10-;g]Yin [1,2- b]Fluorenes (455.5mg, 0.50mmol) is dissolved in 12ml toluene, adds palladium (3.93mg, 17.5 μm of ol) and three hexamethylenes 3mL tetraethyl ammonium hydroxides are then added in base phosphine (9.81mg, 35.0 μm of ol), are warming up to 80 DEG C, react 24 hours；Then plus Enter 18.3mg (0.15mmol) phenyl boric acid to be blocked, after 12 hours, then be blocked with 47.1mg (0.30mmol) bromobenzene；After After continuing reaction 12 hours, stop reaction, wait for that temperature is down to room temperature, the precipitating in 300mL methanol is added dropwise in product, is filtered, then Crude product is dissolved in the toluene of 20mL, is that eluant, eluent carries out column chromatography with toluene using 200~300 mesh silica gel as stationary phase, it is molten Agent concentrates, and separates out come in methyl alcohol again, stirs, and filtering obtains polymer solids after vacuum drying；Finally use first successively again Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, The fibrous solids polymer P 3 obtained after vacuum drying.1H NMR, GPC and elemental analysis are the result shows that obtained polymer For target product, preparation process chemical equation is as follows：
The synthesis of 4 polymer P 4 of embodiment
(1) synthesis of hexamethylene -1,4- dicarbapentaborane-two (3- bromophenyls) hydrazone
With 200ml ethyl alcohol dissolving 3- bromobenzenes hydrazine hydrochloride (11.2g, 50mmol) and sodium acetate (4.1g, 50mmol), stirring It is uniformly mixed；Under protection of argon gas, the ethanol solution (100ml) of Isosorbide-5-Nitrae-cyclohexanedione (2.81g, 25mmol) is added, it is then oily Bath is warming up to 60 DEG C, reacts 5 hours；After stopping reaction, reaction solution is poured into ice water, is stirred, separation filter cake is filtered, ice is used in combination Ethyl alcohol washs, and obtains brown solid, yield 75%, low-temperature dark is handled after solid drying, is directly used in next step without processing Reaction.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, chemical equation As follows：
(2) bis- bromo indoles of 3,9-;3,2-b]The synthesis of carbazole：
With 100ml glacial acetic acid/- two (3- bromines of concentrated sulfuric acid mixed solution (volume ratio 4/1) dissolving hexamethylene -1,4- dicarbapentaborane 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 ice water, is stirred, separation filter cake is filtered, ice is used in combination Ethyl alcohol washs, and obtains yellowish-brown crude product, DMF is used in combination to be recrystallized to give yellow green needle-like solid, yield 25%.1H NMR、13C The result shows that obtained compound is target product, chemical equation is as follows for NMR, MS and elemental analysis：
(3) 3,9- bis- bromo- 5,11- bis- (9- cetyls) indoles;3,2-b]The synthesis of carbazole：
With bis- bromo indoles of 40ml dmso solutions 3,9-;3,2-b]Carbazole (2.0g, 4.8mmol), tetrabutyl phosphonium bromide Ammonium (154mg, 0.48mmol)；Under protection of argon gas, oil bath is warming up to 60 DEG C, continuously adds the sodium hydroxide (2.7g/ of 50wt% 2.7ml deionized waters, 48mmol) aqueous solution, stirring 1 hour after, rapidly join bromohexadecane (4.4g, 14.2mmol)；Instead After answering 12 hours, reaction solution is poured into ice water, is stirred, separation filter cake is filtered, is used in combination ethyl alcohol to wash, obtains yellow solid, produce Rate 91%.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, chemical reaction equation Formula is as follows：
(4) 3,9- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl) -5,11- two (9- cetyls) Yin Duo [3,2-b]The synthesis of carbazole：
3,9- bis- bromo- 5,11- bis- (9- heptadecyls) indoles is dissolved with 50ml dioxane solutions;3,2-b]Carbazole (1.0g, 1.1mmol) and duplex pinacol borate (0.9g, 3.5mmol), under protection of argon gas, oil bath is warming up to 80 DEG C, adds Enter 1,1 '-bis- diphenylphosphine ferrocene palladium chlorides (40mg, 55 μm of ol), reacts 12 hours；It is after stopping reaction, reaction solution is dense Contracting, is extracted with ethyl acetate three times successively, dry after organic phase is washed with deionized three times, concentration, crude product silica gel column layer Analysis method separating-purifying, petrol ether/ethyl acetate (5/1, v/v) mixed solvent obtain faint yellow solid as eluent.Yield 56%.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, chemical equation As follows：
(5) polymer P 4 synthesizes：
Under argon gas protection, by 3,9- bis- (4,4 ', 5,5 '-tetramethyls -1,3,2- dioxaborinates-diyl) -5,11- bis- (9- cetyls) Yin Duo [3,2-b]Tetra- n-hexyl of carbazole (478.6mg, 0.50mmol) and bis- bromo- 7,7,13,13- of 5,10-- 7,13- Er Qingbenbings [g]Yin [1,2-b]Fluorenes (455.5mg, 0.50mmol) is dissolved in 12ml toluene, adds palladium 3mL tetraethyl ammonium hydroxides, heating is then added in (3.93mg, 17.5 μm of ol) and tricyclohexyl phosphine (9.81mg, 35.0 μm of ol) To 80 DEG C, react 24 hours；Then 18.3mg (0.15mmol) phenyl boric acid is added to be blocked, after 12 hours, then uses 47.1mg (0.30mmol) bromobenzene is blocked；After the reaction was continued 12 hours, stops reaction, wait for that temperature is down to room temperature, product is added dropwise The precipitating in 300mL methanol, filtering, then crude product is dissolved in the toluene of 20mL, using 200~300 mesh silica gel as stationary phase, use Toluene is that eluant, eluent carries out column chromatography, and solvent concentration separates out come again in methyl alcohol, stirs, and filtering obtains after vacuum drying Polymer solids；It is finally respectively extracted 24 hours with methanol, acetone, tetrahydrofuran successively again, removes small molecule；By four after concentration Hydrogen tetrahydrofuran solution instills precipitating in methanol, the fibrous solids polymer P 4 obtained after vacuum drying.1H NMR, GPC and element Analysis result shows that obtained polymer is target product, and preparation process chemical equation is as follows：
The synthesis of 5 polymer P 5 of embodiment
(1) 2,2 '-(tetra- n-hexyl -7,13- Er Qingbenbings &#91 of 7,7,13,13-;g]Yin [1,2-b]Fluorenes -5,11- diyls) two The synthesis of (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates)
With bis- bromo- 7,7,13,13- of 50ml dioxane solutions dissolving 5,10-, tetra- n-hexyl -7,13- dihydrobenzos;g]Indenes [1,2-b]Fluorenes (2.0g, 2.2mmol) and duplex pinacol borate (1.8g, 7.0mmol), under protection of argon gas, oil bath heating To 80 DEG C, 1,1 '-bis- diphenylphosphine ferrocene palladium chlorides (80mg, 110 μm of ol) are rapidly joined, are reacted 12 hours；Stop anti- Ying Hou concentrates reaction solution, is extracted with ethyl acetate successively three times, dry after organic phase is washed with deionized three times, dense Contracting, crude product silica gel column chromatography separating-purifying, petrol ether/ethyl acetate (5/1, v/v) mixed solvent obtain white as eluent Color solid.Yield 56%.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, chemistry Reaction equation is as follows：
(2) synthesis of 3,6- bis- (4- bromophenyls)-pyrrolopyrrole -1,4- diketone
Under argon gas protection, by metallic sodium (2.3g, 0.1mol), FeCl3(56mg, 1mmol) is added in tert-pentyl alcohol (50mL), 90 DEG C are warming up to, 1h is stirred.Sodium all after dissolving, is cooled to 50 DEG C, 4- Brominals (6.56g, 36mmol) is added, then be warming up to 90℃.The tert-amyl alcohol solution 10mL of diisopropyl ester amber acid (2.91g, 14.4mmol) is added dropwise dropwise.It is cold after isothermal reaction 20h But to 50 DEG C, 15mL glacial acetic acid is added, then is warming up to 120 DEG C of reaction 4h.After stopping reaction, carried out repeatedly with hot methanol/hot water It rinses and filters, red solid is obtained after drying.Yield 82%.1H NMR、13C NMR, MS and elemental analysis are the result shows that obtained change Conjunction object is target product, and chemical equation is as follows：
(3) synthesis of 2,5- heptacosanes base -3,6- two (4- bromophenyls)-pyrrolopyrrole -1,4- diketone
By 3,6- bis- (4- bromophenyls)-pyrrolopyrrole-Isosorbide-5-Nitrae-diketone (4.4g, 9.86mmol), Anhydrous potassium carbonate (1.82g, 16mmol) and 18- crown ethers -6 (130mg, 0.49mmol) and 120ml DMF are added in reaction bulb.When temperature stablize to At 120 DEG C, l- bromines heptadecane (4.0g, 12mmol) is added into system.Stop reaction after 6h, is cooled to room temperature.With a large amount of water, Dichloromethane extracts three times, collects organic phase, concentration, anhydrous magnesium sulfate drying, crude product silica gel column chromatography separating-purifying, stone Oily ether/dichloromethane (20/1, v/v) mixed solvent obtains orange solids as eluent.Yield 52%.1H NMR、13C NMR、 The result shows that obtained compound is target product, chemical equation is as follows for MS and elemental analysis：
(4) synthesis of polymer P 5
Under argon gas protection, by 2,5- heptacosanes base -3,6- bis- (4- bromophenyls)-pyrrolopyrrole-Isosorbide-5-Nitrae-diketone (475.5mg, 0.50mmol) and 2,2 '-(tetra- n-hexyl -7,13- Er Qingbenbings &#91 of 7,7,13,13-;g]Yin [1,2-b]Fluorenes -5, 11- diyls) two (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates) (502.6mg, 0.50mmol) are dissolved in 12ml toluene In, palladium (3.93mg, 17.5 μm of ol) and tricyclohexyl phosphine (9.81mg, 35.0 μm of ol) are added, 3mL tetrems are then added Base ammonium hydroxide is warming up to 80 DEG C, reacts 24 hours；Then 18.3mg (0.15mmol) phenyl boric acid is added to be blocked, 12 is small Shi Hou, then blocked with 47.1mg (0.30mmol) bromobenzene；After the reaction was continued 12 hours, stops reaction, wait for that temperature is down to Product is added dropwise the precipitating in 300mL methanol, filtering, then crude product is dissolved in the toluene of 20mL by room temperature, with 200~300 mesh Silica gel is stationary phase, is that eluant, eluent carries out column chromatography with toluene, solvent concentration separates out come again in methyl alcohol, stirring, mistake Filter, polymer solids are obtained after vacuum drying；It is finally respectively extracted 24 hours, is removed small with methanol, acetone, tetrahydrofuran successively again Molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the fibrous solids polymer P 5 obtained after vacuum drying 。1H NMR, GPC and elemental analysis the result shows that obtained polymer be target product, preparation process chemical equation As follows：
The synthesis of 6 polymer P 6 of embodiment
(1)N1,N4- two (4- n-octyls)-N1,N4The synthesis of diphenyl benzene -1,4- diamines：
It is dissolved full liquid dissolving 4- octyls bromobenzene (6.19g, 23mmol) and N with 150ml toluene1,N4Diphenyl benzene -1,4- two Amine (2.60g, 10mmol) adds tertiary butyl sodium alkoxide (3.94g, 41mmol) and palladium (96mg, 0.5mmol), in argon gas Under protection, oil bath is warming up to 85 DEG C, continuously adds the toluene solution (2.0mol/L, 0.5mL) of tri-tert-butylphosphine；Reaction 12 hours Afterwards, it adds water in reaction solution and reaction is quenched, three times with dichloromethane extraction, after organic phase is washed with deionized three times, do Dry, concentration, crude product silica gel column chromatography separating-purifying, pure petroleum ether obtains white solid as eluent.Yield 82%.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, the following institute of chemical equation Show：
(2)N1,N4- two (4- bromophenyls)-N1,N4The synthesis of-two (4- n-octyls phenyl) -1,4- diamines：
It is completely dissolved N with 20ml N,N-dimethylformamides1,N4- two (4- n-octyls)-N1,N4Diphenyl benzene -1, The N of N- bromo-succinimides (NBS, 2.74g, 15.4mmol) is added dropwise under the conditions of 0 DEG C in 4- diamines (4.46g, 7mmol), Dinethylformamide (DMF) solution reacts 4 hours under the conditions of being protected from light；Reaction solution is poured into water, is stirred, filtering, filter cake is used Silica gel column chromatography separating-purifying, pure petroleum ether obtain white solid as eluent.Yield 81%.1H NMR、13C NMR、 The result shows that obtained compound is target product, chemical equation is as follows for MS and elemental analysis：
(3)N1,N4- two (4- n-octyls phenyl)-N1,N4- two (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates - Diyl)-phenyl) benzene -1,4- diamines synthesis：
It is completely dissolved N with 100ml anhydrous tetrahydro furans (THF) solution1,N4- two (4- bromophenyls)-N1,N4- two (4- is just pungent Base phenyl)-Isosorbide-5-Nitrae-diamines (3.91g, 5mmol) is cooled to -78 DEG C under protection of argon gas, the n-BuLi of 5.3ml is added dropwise Hexane solution (a concentration of 2.4mol L-1), after reacting 1 hour, it is added at one time 2- isopropoxies -4,4,5,5- tetramethyls Base -1,3,2- ethylenedioxies borate (2.6g, 14mmol) continue stirring 2 hours；Reaction system is gradually increased to normal-temperature reaction 24 Hour；Reaction solution is concentrated, is extracted with ethyl acetate successively three times, it is dry after organic phase is washed with deionized three times, it is dense Contracting, crude product silica gel column chromatography separating-purifying, petroleum ether/dichloromethane (4/1, v/v) mixed solvent are obtained as eluent White solid.Yield 69%.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, change It is as follows to learn reaction equation：
(4) polymer P 6 synthesizes：
Under argon gas protection, by N1,N4- two (4- n-octyls phenyl)-N1,N4- two (4,4 ', 5,5 '-tetramethyl -1,3,2- two Oxa- borine-diyl)-phenyl) benzene -1,4- diamines (444.4mg, 0.50mmol) and bis- bromo- 7,7,13,13- tetra- of 5,10- just oneself Base -7,13- Er Qingbenbings [g]Yin [1,2-b]Fluorenes (455.5mg, 0.50mmol) is dissolved in 12ml toluene, adds palladium 3mL tetraethyl ammonium hydroxides, heating is then added in (3.93mg, 17.5 μm of ol) and tricyclohexyl phosphine (9.81mg, 35.0 μm of ol) To 80 DEG C, react 24 hours；Then 18.3mg (0.15mmol) phenyl boric acid is added to be blocked, after 12 hours, then uses 47.1mg (0.30mmol) bromobenzene is blocked；After the reaction was continued 12 hours, stops reaction, wait for that temperature is down to room temperature, product is added dropwise The precipitating in 300mL methanol, filtering, then crude product is dissolved in the toluene of 20mL, using 200~300 mesh silica gel as stationary phase, use Toluene is that eluant, eluent carries out column chromatography, and solvent concentration separates out come again in methyl alcohol, stirs, and filtering obtains after vacuum drying Polymer solids；It is finally respectively extracted 24 hours with methanol, acetone, tetrahydrofuran successively again, removes small molecule；By four after concentration Hydrogen tetrahydrofuran solution instills precipitating in methanol, the fibrous solids polymer P 6 obtained after vacuum drying.1H NMR, GPC and element Analysis result shows that obtained polymer is target product, and preparation process chemical equation is as follows：
Embodiment 7
Conjugated polymer two-photon absorption performance test based on naphtho- indenes fluorenes unit
As two-photon fluorescence revulsion to double light of the conjugated polymer based on naphtho- indenes fluorenes unit obtained by the present invention Sub- absorbent properties are tested；Pump light is used as using ti:sapphire laser femto-second laser (Avesta TiF-100M) when experiment test The pulse width in source, laser is 80fs, frequency 84.5Hz；The thang-kng length of pulse is the quartz sample pool of 10mm.Polymer P1 is dissolved in the solvent of four kinds of opposed polarities, respectively toluene, tetrahydrofuran, dichloromethane, n,N-Dimethylformamide；It is poly- It closes object P2~P4 to be dissolved in toluene, the concentration of all solution is 1 × 10-6mol L-1.Standard specimen is the 0.1mol L of fluorescein-1Sodium hydrate aqueous solution, a concentration of 1 × 10-6mol L-1, fluorescence quantum yield 88%.
Polymer P 1-P4 is as shown in table 1 in the fluorescence quantum yield test result of solution state.
Table 1
As known from Table 1, the fluorescence quantum yield of polymer P 1 is 83% under toluene solution state, as solvent polarity increases Add, by low pole toluene to highly polar n,N-Dimethylformamide, fluorescence quantum yield gradually decreases to 11%.This illustrates to polymerize Object P1 has stronger two-photon response potentiality in low pole toluene solution.Also turn out that the polarity of solvent is to influence polymerization simultaneously One key factor of object two-photon response.The fluorescence quantum yield of 2~P5 of polymer P is respectively in toluene solvant 61%, 73%, 66% and 83%, higher fluorescence quantum yield illustrates polymer in two-photon fluorescence microtechnic, two-photon Up-conversion lasing, optical Limiting, double photon three dimension processing, double photon three dimension optical storage, double-photon optical photodynamic therapy etc. There is excellent application prospect.
The two photon absorption cross section of polymer 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 indicates standard specimen, the 0.1mol L of fluorescein-1Sodium hydrate aqueous solution；2 indicate sample to be tested. I1、I2Indicate standard specimen, sample to be tested two-photon fluorescence spectrum integral area, two-photon fluorescence spectrogram is shown in Fig. 2, Fig. 3. φ1、φ2Indicate the fluorescence quantum efficiency of standard specimen, sample to be tested.C1、C2Indicate the solution concentration of standard specimen, sample to be tested.
Two photon absorption cross section of the polymer P 1 in low pole toluene solvant and middle polarity dichloromethane solvent with swash The relational graph of optical wavelength is as shown in Figure 3.It can be seen from the figure that under opposed polarity solvent state, the two-photon of polymer P 1 Absorption cross-section is similar with the variation tendency of optical maser wavelength, with the increase of optical maser wavelength, the two photon absorption cross section of polymer P 1 First increase to reduce afterwards and reduce after increase.When optical maser wavelength is 730nm, the two photon absorption cross section of polymer is maximum, toluene It is 6437GM (1GM=10 in solvent-50cm-4s photon-1), it is 3497GM in dichloromethane；When optical maser wavelength is 830nm When, the two photon absorption cross section time of polymer is big, is 2969GM in toluene solvant, is 1229GM in dichloromethane；And dichloromethane Two photon absorption cross section in alkane is generally lower than in toluene solvant, this fluorescence quantum yield in methylene chloride with polymer P 1 Matching lower than in toluene solution, this explanation, fluorescence quantum yield be influence one of material two photon absorption cross section value size because Element：
Polymer P 1 has larger two photon absorption cross section value in entire test scope, illustrates to be based on naphtho- indenes fluorenes list The conjugated polymer of member has good two-photon response, in nonlinear optics and biological imaging field practical application valence Value.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other it is any without departing from spirit of the invention under principle made by changes, modifications, substitutions, combinations, simplifications should be Equivalent substitute mode, is included within the scope of the present invention.

Claims (10)

1. a kind of conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes, which is characterized in that the polymer formulae is as follows：
In formula, n=1~1000；R is C1~C30Straight chain or branched alkyl or be C1~C30Alkoxy or be benzene oxygen Base.
2. conjugated polymer of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes according to claim 1, which is characterized in that The Ar is any one in following structural formula：
Wherein, R1~R6Can be identical or different, it is independently selected from H, C1~C30Straight chain or branched alkyl or be C1~C30's Alkoxy is phenoxy group.
3. the method for preparing a kind of conjugated polymer based on the high two-photon absorption of naphtho- indenes fluorenes as claimed in claim 1 or 2, It is characterized in that, includes the following steps：
(1) under inert gas protection, it is completely dissolved the monomer of naphtho- indenes fluorenes unit and the structure containing Ar with organic solvent, is being catalyzed Agent effect and tetraethyl ammonium hydroxide effect under, be heated to 60~100 DEG C generation Suzuki polymerisations, the reaction time be 12~ 36h；
(2) it is added phenyl boric acid into reaction solution obtained by step (1), 60~100 DEG C of constant temperature the reaction was continued 6~12h；Add bromobenzene 60~100 DEG C of continuation 6~12h of isothermal reaction, reaction purify gained reaction solution to get based on naphtho- indenes fluorenes Gao Shuanguang after stopping The conjugated polymer that son absorbs；
Synthetic route is as follows
4. preparation method according to claim 3, which is characterized in that step (1) described inert gas is argon gas；It is described to have Solvent is at least one of toluene, tetrahydrofuran, dimethylbenzene, dioxane and N,N-dimethylformamide.
5. preparation method according to claim 3, which is characterized in that the catalyst is the combination in palladium source and phosphine source；Institute It is one kind in palladium and tris(dibenzylideneacetone) dipalladium to state palladium source；The phosphine source is thricyclohexyl phosphorus, four triphenylphosphines At least one of palladium and triphenylphosphine palladium.
6. preparation method according to claim 3, which is characterized in that naphtho- indenes fluorenes unit described in step (1) is tied containing Ar The dosage of the monomer of structure meets the monomer integral molar quantity containing double borate functional groups or containing double boric acid functional groups and contains double bromine functions The monomer integral molar quantity of group or the functional group containing Shuan Dian is equal.
7. preparation method according to claim 3, which is characterized in that the dosage of step (1) described catalyst is that reaction is single 5 ‰~the 3% of body moles total number.
8. preparation method according to claim 3, which is characterized in that the dosage of the phenyl boric acid described in step (2) is reaction The 10~20% of monomer molar total amount.
9. preparation method according to claim 3, which is characterized in that the dosage of the bromobenzene described in step (2) is phenyl boric acid 2~5 times of mole.
10. conjugated polymer of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes as claimed in claim 1 or 2 is in two-photon fluorescence Micro-, two-photon up-conversion lasing, optical Limiting, double photon three dimension processing, double photon three dimension optical storage and double-photon optical power Learn the application in treatment.
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