CN104877666A - Luminescent material having aggregation-induced emission, method of making and application thereof - Google Patents
Luminescent material having aggregation-induced emission, method of making and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 230000002776 aggregation Effects 0.000 title claims abstract description 41
- 238000004220 aggregation Methods 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 230000003287 optical effect Effects 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- -1 azido- Chemical class 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
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- 230000008569 process Effects 0.000 claims description 9
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- 239000007858 starting material Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 238000003384 imaging method Methods 0.000 claims description 7
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- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
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- 239000000243 solution Substances 0.000 description 21
- 238000005424 photoluminescence Methods 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
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- IGFKZONLWYOOPL-UHFFFAOYSA-N 2,5-dihexoxy-4-[2-[4-(1,2,2-triphenylethenyl)phenyl]ethynyl]benzaldehyde Chemical compound C(CCCCC)OC1=C(C=O)C=C(C(=C1)C#CC1=CC=C(C=C1)C(=C(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)OCCCCCC IGFKZONLWYOOPL-UHFFFAOYSA-N 0.000 description 1
- GEVHYMHXSIAZHL-UHFFFAOYSA-N 5-[[4-(1,2,2-triphenylethenyl)phenyl]methylidene]-1,3-diazinane-2,4,6-trione Chemical compound C1(=CC=CC=C1)C(=C(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=C(C=C2C(NC(NC2=O)=O)=O)C=C1 GEVHYMHXSIAZHL-UHFFFAOYSA-N 0.000 description 1
- YJADROSYDFWBOK-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(S(C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C=1C(=C(S(C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 YJADROSYDFWBOK-UHFFFAOYSA-N 0.000 description 1
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- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a luminescent material having aggregation-induced emission, a method of making and an application thereof. The luminescent material herein has properties of aggregation-induced emission (AIE)/aggregation-enhanced emission (AEE) with the maximum absorption wavelength red shift to a visible area so that this type of luminescent material has the potential applications in the field of biology and photoelectricity. The luminescent material herein also has excellent optical waveguide property with an optical loss lower to 0.100dB/[mu]m, and is applicable to produce optical waveguide materials and also applicable to organic light emitting diodes. The luminescent material herein also has the characteristic of mechanochromism and reversible mechanochromism, thus having potential application in the aspect of smart materials.
Description
Technical field
The present invention relates to a series of luminous organic material, be specifically related to the solid luminescent material with aggregation-induced emission or luminescence enhancement (AIE/AEE) characteristic.
Background technology
Along with the development of organic optoelectronic, at the novel organic luminous semiconductor functional materials that solid-state or state of aggregation use, due to compared with traditional inorganic semiconductor material, there is high sensitivity, good device flexibility, low cost, dingus size, big area preparation and be convenient to the advantages such as integrated, and being subject to increasing concern (Chem.Phys.Lett., 1974,29,277, Chem.Rev.2007,107,1011).Except organic optoelectronic device, luminous organic material stores (J.Mater.Chem.C, 2013,1,3376 in information; Chem.Soc.Rev., 2013,42,857; Adv.Mater., 2013,25,378; Chem.Soc.Rev., 2013,42,8895.) and bio-science (Chem.Rev., 2013,113,192; Chem.Sci., 2012,3,984.) etc. aspect also shows and applies widely.
But, conventional organic luminescence material is always attended by inevitable phenomenon: assemble and cause cancellation (aggregation-caused quenching, ACQ), traditional fluorescent material is usually containing larger π-electron conjugated structure, and this structure is mainly for generation of fluorescence.Under molecular melting state, the solution of fluorescence dye demonstrates hyperfluorescenceZeng Yongminggaoyingguang, but strong solution state, state of aggregation or solid-state time, intermolecular interaction strengthens, energy trasfer occurs, and form exciplex or excimer, these all can consume excited energy, therefore the possibility of fluorescence radiation is greatly reduced, well-known ACQ phenomenon that Here it is.But in modern technologies application, in most cases, fluorescent material needs to be processed into state of aggregation, and ACQ problem is inevitable.Various chemistry (Chem.Commun., 2008,1501 are developed at present; Chem.Commun., 2008,217.), physics and engineering method and the course of processing (Langmuir, 2006,22,4799; Macromolecules 2003,36,5285) to weaken ACQ effect, but these trials only can obtain less success, main difficulty is that the formation of aggregate is an intrinsic procedure in condensed phase, is therefore badly in need of exploitation and keeps strong luminous materials and systems in the collected state.
In calendar year 2001, researchist of the present invention has synthesized 1, 1-dimethyl-2, 3, 4, 5-tetraphenyl thiophene coughs up (DMTPS) compound, its state of aggregation plays useful but not destructive effects (Chem.Commun.2001 in fluorescence radiation, 1740.), researchist also observes a kind of novel phenomenon and hat is called " focusing induced luminescence " (aggregation-induced emission, AIE), under solution state, non-luminous molecule is formed by aggregate and is induced luminescence: a series of spiral helicine non-luminescent molecule, as hexaphenyl thiophene coughs up (HPS) and tetraphenyl ethylene (tetraphenylethene, TPE), be induced to send very strong fluorescence (J.Mater.Chem.2001 by forming aggregate, 11, 2974, Chem.Commun.2009,4332, Appl.Phys.Lett.2007,91,011111.), investigators have found a variety of molecule with this characteristic afterwards.In addition, designed and Theoretical Calculation by series of experiments, investigators confirm that internal molecular motion limited (RIM) is the major cause (J.Phys.Chem.B2005,109,10061 that cause AIE effect; J.Am.Chem.Soc.2005,127,6335.).
So far, most of AIE twinklers of preparation can only launch blue light and green glow, compared with blue-light emitting material, relatively lag behind to the R and D of the material of gold-tinted and ruddiness, and in organic integrated circuits, and gold-tinted and red light material are absolutely necessary assembly; Equally for the application of bio-imaging aspect, more preferably those longwave transmissions dye molecule, the interference of the autofluorescence of biological tissue can not be subject to like this, and the damage of excitation light source to tissue also will reduce (Chem.Mater., 2012,24,812).For the preparation of gold-tinted and green light material, method of the prior art be extend molecule pi-conjugated structure so that reduce band gap and be beneficial to transition of electron, but this method weak point is that building-up process is complicated, synthetic work amount large, molecular interaction strengthens thus easily causes induced luminescence cancellation, is subject to the problem such as photoxidation impact and the reduction of product solubleness.
Summary of the invention
The object of this invention is to provide and a kind of there is luminescent material of aggregation-induced emission characteristic and its preparation method and application, solve the luminescent material with aggregation-induced emission characteristic of the prior art and apply limited problem.
The technical scheme that technical solution problem of the present invention adopts is: a kind of luminescent material with aggregation-induced emission characteristic, includes the group being selected from following arbitrary structural formula:
Wherein, R
1, R
2and R
3be selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, alkoxyl group, aryloxy, carboxyl, lsothiocyanates group, azido-, alkyl diazoimide base, alkylamino, chloro alkyl, bromo alkyl, iodo-alkyl, ester group respectively, R
1, R
2and R
3following structural formula can also be selected from respectively:
or
wherein Y is O, S or Se; R
1and R
2be respectively the alkyl of-H, line style or branching type, R
3and R
4be respectively alkyl or the alkoxyl group of line style or branching type;
In structural formula I and II, respectively at least containing a R
1, R
2or R
3; Y is O, S or Se; R
1and R
2be respectively the alkyl of line style or branching type; R
3and R
4be respectively alkyl or the alkoxyl group of line style or branching type;
Tetraphenyl ethylene unit in structural formula I and II at least comprises one, and is connected by C-C singly-bound, C=C double bond or C ≡ C triple bond.
Have in the luminescent material of aggregation-induced emission characteristic of the present invention, R
1, R
2and R
3be-H; Y is O.
Have in the luminescent material of aggregation-induced emission characteristic of the present invention, in structural formula I, R
1and R
2be selected from-H or alkyl respectively and R
1and R
2it is identical group; In formula II, R
1and R
2be-H, R
3and R
4be selected from alkyl or alkoxyl group respectively and R
3and R
4it is identical group.
Have in the luminescent material of aggregation-induced emission characteristic of the present invention, in structural formula I, R
1and R
2be-H or be-CH
3group; In formula II, R
3and R
4be-CH
3or-OC
6h
13group.
The present invention also provides the above-mentioned luminescent material with aggregation-induced emission characteristic preparing the application in optical waveguide material.
The present invention also provides the above-mentioned luminescent material with aggregation-induced emission characteristic preparing the application in oled device.
The present invention also provides the above-mentioned luminescent material with aggregation-induced emission characteristic preparing the application of fluorescent dye of imaging in cell.
The present invention also provides the above-mentioned preparation method with the luminescent material of aggregation-induced emission characteristic, comprise the steps: as the tetraphenyl ethylene derivative of start material and barbituric acid compounds heating reflux reaction in organic alcohol solvent, form throw out, throw out is filtered, product organic solvent washing after filtration, vacuum-drying obtains luminescent material;
The structural formula of the tetraphenyl ethylene derivative in wherein said start material is:
or
Wherein, R
1, R
2and R
3be selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, alkoxyl group, aryloxy, carboxyl, lsothiocyanates group, azido-, alkyl diazoimide base, alkylamino, chloro alkyl, bromo alkyl, iodo-alkyl, ester group respectively, R
1, R
2and R
3following structural formula can also be selected from respectively:
or
wherein Y is O, S or Se; R
1and R
2be respectively the alkyl of-H, line style or branching type, R
3and R
4be respectively alkyl or the alkoxyl group of line style or branching type;
In the structural formula of the tetraphenyl ethylene derivative in start material, respectively at least containing a R
1, R
2or R
3; Tetraphenyl ethylene unit wherein at least comprises one, and is connected by C-C singly-bound, C=C double bond or C ≡ C triple bond.
In the preparation process in accordance with the present invention, the barbituric acid compounds in described start material is barbituric acid or N, N-dimethyl barbituric acid; Described organic alcohol solvent is methyl alcohol or ethanol; Described organic solvent is selected from least one in methyl alcohol, ethanol, ether; Described throw out can filtered while hot or be cooled to room temperature and carry out filtration and obtain solid.
In the preparation process in accordance with the present invention, be also included in the process of heating reflux reaction and add the step of the vitriol oil as catalyzer; And rear ether and the hexane of using of product washing after filtering is carried out the step of recrystallization to the product filtered.
It should be noted that, described alkyl can be straight chain type, can be also branched chain type, containing 1-10 carbon atom in chain, preferably containing the alkyl of 2-6 carbon atom; Described cycloalkyl refers to the monocycle of non-aromatics or many rings, containing 3-10 carbon atom; Described assorted alkyl refer at least one carbon atom in alkyl replace by heteroatoms; Heterocyclylalkyl refers to that in the cycloalkyl of 3-7 ring, at least one ring is heteroatoms, and this heteroatoms is selected from O, N, S, Si and B; Aryl preferably contains 6-18 carbon atom, as phenyl, naphthyl, anthryl, tetracene group, pyrene group; Have at least a ring to be heteroatoms in aryl containing 5-10 ring, this heteroatoms is selected from O, N, S, Si and B.
Implement luminescent material and the application thereof with aggregation-induced emission characteristic of the present invention, there is following beneficial effect: luminescent material of the present invention has the aggregation inducing/enhancing characteristics of luminescence (aggregation-induced/enhanced emission, AIE/AEE), dispersion embodies AIE/AEE characteristic in an aqueous medium; It absorbs red shift to visibility region, and then improve the application possibility of luminescent material in biology and photoelectronics; The THF/H of 90% is greater than at water-content
2can nanoparticle be formed in O mixed solvent, after this nanoparticle is coated by albumen, enter cell; In grinding-stifling and grinding-heat-processed, due to molecular conformation crystal and amorphous between change, cause glow color reversible transition; Self-assembly nanometer ball, nanometer rod and nanotube can be formed in different solvents under not adding trimeric cyanamide and adding trimeric cyanamide condition; Have splendid optical waveguides character, optical loss coefficient is low to moderate 0.137dB/ μm, can be used for preparing optical waveguide material; In view of the good solid luminescent character of such material, also may be used for preparing oled device.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of TPE-s-Bar, TPE-Bar, TPE-MPh-Bar and TPE-HPh-Bar;
Fig. 2 is the ORTEP figure of TPE-s-Bar;
Fig. 3 A is the THF/H of TPE-s-Bar at different water-content (vol%)
2photoluminescence (PL) spectrogram in O solvent, wherein illustration is the I/I of TPE-s-Bar
0and the correlogram in system between water-content, I
0for the maximum PL intensity of TPE-s-Bar in pure THF, concentration is 10 μMs, and excitation wavelength is 420nm;
Fig. 3 B is the THF/H of TPE-Bar at different water-content (vol%)
2photoluminescence (PL) spectrogram in O solvent, wherein illustration is the I/I of TPE-Bar
0from the correlogram between different water-content, I
0the maximum PL intensity of=TPE-Bar in pure THF, concentration is 10 μMs, and excitation wavelength is 420nm;
Fig. 3 C is the THF/H of TPE-MPh-Bar at different water-content (vol%)
2photoluminescence (PL) spectrogram in O solvent, wherein illustration is the I/I of TPE-MPh-Bar
0from the correlogram between different water-content, I
0the maximum PL intensity of=TPE-MPh-Bar in pure THF, concentration is 10 μMs, and excitation wavelength is 410nm;
Fig. 4 A is that TPE-HPh-Bar is at different water-content (f
w) THF/H
2photoluminescence (PL) spectrogram in O solvent, wherein concentration is 10 μMs, and excitation wavelength is 447nm;
Fig. 4 B is the relative PL intensity I/I of TPE-HPh-Bar
0with THF/H
2the correlogram of O composition, I
0for the luminous intensity of TPE-MPh-Bar in pure THF (emission intensity), illustration is that TPE-HPh-Bar is respectively the THF/H of 0vol% and 95vol% at water-content
2the fluorescence photo that the solution formed in O system obtains under UV-irradiation;
Fig. 5 A is that TPE-s-Bar crystal fumigates the variation diagram of emmission spectrum in process at grinding-solvent;
Fig. 5 B fumigates by repeating grinding-solvent the solid luminescent repetition transition diagram that circulation makes TPE-s-Bar;
Fig. 6 A is that TPE-Bar fumigates the variation diagram of emmission spectrum in process at grinding-solvent;
Fig. 6 B fumigates by repeating grinding-solvent the repetition transition diagram that circulation makes the solid state fluorescence of TPE-Bar;
Fig. 7 A is that TPE-MPh-Bar fumigates the variation diagram of emmission spectrum in process at grinding-solvent;
Fig. 7 B fumigates by repeating grinding-solvent the repetition transition diagram that circulation makes the solid state fluorescence of TPE-MPh-Bar;
Fig. 8 A is that the temperature rise rate of TPE-s-Bar when different state of aggregation is with 10 DEG C of min
– 1xRD diffractogram;
Fig. 8 B is that the temperature rise rate of TPE-s-Bar when different state of aggregation is with 10 DEG C of min
– 1dSC thermogram;
Fig. 9 A is that the temperature rise rate of TPE-Bar when different state of aggregation is with 10 DEG C of min
– 1xRD diffractogram;
Fig. 9 B is that the temperature rise rate of TPE-Bar when different state of aggregation is with 10 DEG C of min
– 1dSC thermogram;
Figure 10 A is the SEM image of micron ball and the nanometer ball formed after the TPE-HPh-Bar solution of 100 μMs is slowly volatilized by solvent in acetonitrile;
Figure 10 B is the SEM image of micron ball and the nanometer ball formed after the TPE-HPh-Bar solution of 10 μMs of concentration is slowly volatilized by solvent in acetonitrile;
Figure 10 C is that the TPE-HPh-Bar solution of 50 μMs of concentration is slowly volatilized by solvent under room temperature condition in acetonitrile/ethanol (1:1v/v) the SEM image of the nanometer ball formed;
Figure 10 D is that the TPE-HPh-Bar solution of 50 μMs of concentration is slowly volatilized by solvent under room temperature condition in the acetonitrile/water (1:1v/v) the SEM image of the nanometer ball formed;
Figure 11 A is under the condition of the trimeric cyanamide adding 10 equivalents, the SEM image of the micron ball that the TPE-HPh-Bar solution of 100 μMs of concentration is formed by solvent slow evaporation under room temperature condition in (1:1v/v) in DMSO/ ethanol and nanometer ball, scale: 5 μm;
Figure 11 B is under the condition adding the trimeric cyanamide having 10 equivalents, the SEM image of the micron ball that the TPE-HPh-Bar solution of 100 μMs of concentration is formed by solvent slow evaporation under room temperature condition in (1:1v/v) in DMSO/ ethanol and nanometer ball, scale: 1 μm;
Figure 11 C is under the condition adding the trimeric cyanamide having 25 equivalents, the SEM image of the micron ball that the TPE-HPh-Bar solution of 100 μMs of concentration is formed by solvent slow evaporation under room temperature condition in (1:1v/v) in DMSO/ ethanol and nanometer ball, scale: 2 μm;
Figure 11 D is under the condition adding the trimeric cyanamide having 25 equivalents, the TPE-HPh-Bar solution of 100 μMs of concentration is slowly volatilized by solvent under room temperature condition in (1:1v/v) the SEM image of the micron ball that formed and nanometer ball in DMSO/ ethanol, scale: 1 μm;
Figure 12 A assembles UV laser (400nm) excites the TPE-s-Bar micron bar obtained microscopic imaging fluorescence photo at seven different positionss;
Figure 12 B is the PL spectrum that the right side rod end recorded TPE-s-Bar micron bar in 12A is marked with the micron bar of a-g;
Figure 12 C is the correlogram of TPE-s-Bar peak intensity and the spacing exciting position and luminous end;
Figure 13 A assembles UV laser (400nm) excites the TPE-HPh-Bar micron bar obtained microscopic imaging fluorescence photo at seven different positionss;
Figure 13 B is the PL spectrum that the right side rod end recorded TPE-HPh-Bar micron bar is in figure 13a marked with the micron bar of a-g;
Figure 13 C is the correlogram of TPE-HPh-Bar peak intensity and the spacing exciting position and luminous end;
Figure 14 is the SEM images of the TPE-HPh-Bar nanoparticle encapsulated by bovine serum albumin, scale: 1 μm.
Embodiment
Below in conjunction with drawings and Examples, the luminescent material having an aggregation-induced emission characteristic to of the present invention and application thereof and preparation method are described further:
The concrete preparation process of luminescent material of aggregation-induced emission characteristic that what the present invention was new have is described by following embodiment.It should be noted that the luminescent material prepared is only one or more of luminescent material in the structural formula I-II protected in claim represented by each structural formula below, but the luminescent material that the present invention protects is not limited to this.
The synthetic route that wherein embodiment 1-4 building-up process is shown in Figure 1.
Embodiment 1: synthesis TPE-Bar
Structural formula:
Chinese chemical name: 5-(4-(1,2,2-triphenyl vinyl) α-tolylene) pyrimidine-2,4,6 (1H, 3H, 5H)-triketone
English language Chemical formula: 5-(4-(1,2,2-triphenylvinyl) benzylidene) pyrimidine-2,4,6 (1H, 3H, 5H)-trione
Synthetic method: by 4-(1,2,2-triphenyl vinyl) phenyl aldehyde 1 (500mg, 1.39mmol) reflux in methyl alcohol 20mL and THF 5mL mixed solvent with barbituric acid 3 (186mg, 1.46mmol) mixture 24h, forms bright yellow precipitate, after reaction mixture is cooled to room temperature, the bright yellow precipitate formed is filtered, solid ethanol after filtration and ether rinse three times respectively, and vacuum-drying obtains product 390mg, and productive rate is 61%.
1h-NMR (400MHz, d
6-DMSO): δ 11.48 (s, 1H), 11.33 (s, 1H), 8.26 (s, 1H), 8.11 (d, J=8.8Hz, 2H), 7.32-7.23 (m, 9H), 7.17 (d, J=8.4Hz, 2H), 7.15-7.09 (m, 6H);
13c-NMR (100MHz, d
6-DMSO): 163.44,161.67,153.99,150.11,147.83,142.77,142.70,142.56,142.23,139.77,133.49,130.68,130.62,130.57,130.40,128.01,127.98,127.81,127.00,126.80,118.32; HR-MS (MALDI-TOF): 470.1635; Elemental Analysis theory C
31h
22n
2o
3: C, 79.13; H, 4.71; N, 5.95: measured value: C, 79.11; H, 4.732; N, 5.88.
Embodiment 2: synthesis TPE-s-Bar
Structural formula:
Chinese chemical name: 1,3-dimethyl-5-(4-(1,2,2-triphenyl vinyl) α-tolylene) pyrimidine-2,4,6 (1H, 3H, 5H)-triketone
English language Chemical formula: 1,3-dimethyl-5-(4-(1,2,2-triphenylvinyl) benzylidene) pyrimidine-2,4,6 (1H, 3H, 5H)-trione
Synthetic method: by 4-(1,2,2-triphenyl vinyl) phenyl aldehyde 1 (500mg, 1.39mmol) and N, N-dimethyl barbituric acid 2 (227mg, 1.46mmol) add a vitriol oil in mixture as catalyzer, backflow 24h in ethanol (20mL), form orange-yellow throw out, after reaction mixture is cooled to room temperature, the orange-yellow throw out formed is filtered, solid ethanol after filtration and ether rinse three times respectively, and vacuum-drying obtains product 480mg, and productive rate is 70%.HR-MS (MALDI-TOF) C
33h
26n
2o
3theoretical value 498.1943; Measured value: 498.1941;
1h-NMR (400MHz, CDCl
3): δ 8.44 (s, 1H), 7.96 (d, 2H), 7.14-7.10 (m, 11H), 7.06-7.01 (m, 6H), 3.40 (s, 3H), 3.36 (s, 3H);
13c-NMR (100MHz, CDCl
3): δ 161.72,159.57,157.86,150.27,148.70,142.24,142.12,142.04,141.90,138.94,133.04,130.34,130.33,130.29,130.24,129.52,126.91,126.88,126.66,126.08,125.83,125.80,115.30,28.07,27.39.
Embodiment 3: synthesis TPE-HPh-Bar
Structural formula:
Step comprises: (1) synthesis TPE-HPh
Chinese chemical name: 2,5-bis-hexyloxy-4-((4-(1,2,2-triphenyl vinyl) phenyl) ethynyl) phenyl aldehyde
English language Chemical formula: 2,5-dihexyloxy-4-((4-(1,2,2-triphenylvinyl) phenyl) ethynyl) benzaldehyde
Synthetic method: add 2-(4-ethynyl phenyl)-1 in two neck round-bottomed flask, 1,2-triphenyl vinyl 4 (1g, 2.81mmol), 4-bromo-2,5-bis-hexyloxybenzaldehyde 6 (1.03g, 2.68mmol), two (triphenylphosphine) palladium chloride (II) (Pd (PPh
3)
2cl
2) (0.089g, 0.126mmol), cuprous iodide (0.024g, 0.121mmol) with triphenylphosphine (0.066g, 0.251mmol), said mixture is vacuumized and takes a breath three times with nitrogen simultaneously and then remove oxygen completely, the new tetrahydrofuran (THF) 30mL of distillation and the triethylamine 10mL without water degasification is injected in above-mentioned reaction flask, under 70 DEG C of conditions, back flow reaction 8h forms throw out, after being cooled to room temperature, the throw out of formation is filtered out, steam except desolventizing by revolving, residue after removing solvent is crossed silicon-dioxide chromatography post, carry out wash-out by n-hexanes/ch (4:1v/v) and obtain orange/yellow solid shape product 1.3g, productive rate 73.4%.MS:660.3(M
+)；
1H NMR(400MHz,CDCl
3)δ10.43(s,1H),7.30(d,2H),7.27(s,1H),7.15(s,1H),7.13-7.08(m,8H),7.06-6.81(m,9H),4.05-4.00(m,4H),1.84-1.79(m,4H),1.50-1.46(m,4H),1.37-1.31(m,8H),0.93-0.85(m,6H)。
(2) TPE-HPh-Bar is synthesized
Chinese chemical name: 5-(2,5-bis-hexyloxy-4-((4-(1,2,2-triphenyl vinyl) phenyl) ethynyl) α-tolylene) pyrimidine-2,4,6 (1H, 3H, 5H)-triketone
English language Chemical formula: 5-(2,5-dihexyloxy-4-((4-(1,2,2-triphenylvinyl) phenyl) ethynyl) benzylidene) pyrimidine-2,4,6 (1H, 3H, 5H)-trione
Synthetic method: add TPE-HPh (500mg in round-bottomed flask, 0.758mmol) with barbituric acid 3 (106mg, 0.828mmol), then methyl alcohol 40mL and THF 5mL is added, said mixture is stirred in nitrogen atmosphere and reflux 24h, form red precipitate, filtered while hot, the filtration product washed with methanol obtained three times, then the red solid obtained is dissolved in ether, add appropriate hexane, then recrystallization obtains crystalline product 0.356g, productive rate 61%.
1h NMR (400MHz, CDCl
3), δ 9.06 (s, 1H), 8.30 (s, 1H), 8.18 (s, 1H), 8.11 (s, 1H), 7.29 (d,
2j=8.4Hz, 2H), 7.13-7.08 (m, 9H), 7.05-7.01 (m, 8H), 6.98 (s, 1H), 4.06-4.02 (m, 4H), 1.86-1.81 (m, 4H), 1.58-1.43 (m, 4H), 1.37-1.29 (m, 8H), 0.92-0.84 (m, 6H);
13cNMR (400MHz, CDCl
3), δ (TMS, ppm): 162.99,160.92,155.18,154.56,152.65,148.80,144.85,143.57,143.51,143.41,142.10,140.33,131.57,131.52,131.47,131.43,131.36,127.98,127.93,127.83,126.88,126.80,122.07,121.84,120.85,116.81,115.61,114.82,98.77,86.59,69.73,69.61,31.73,31.60,29.31,29.17,25.89,25.78,22.75,22.71,14.18,14.14; HRMS (MALDI-TOF) C
51h
50n
2o
5theoretical value 770.3720; Measured value 770.3722. Elemental Analysis theory C
51h
50n
2o
5: C, 79.45; H, 6.54; N, 3.63; Measured value: C, 79.60; H, 6.606; N, 3.59.
Embodiment 4: synthesis TPE-MPh-Bar
Structural formula:
Step comprises: (1) synthesis TPE-MPh
Chinese chemical name: 2,5-dimethyl-4-((4-(1,2,2-triphenyl vinyl) phenyl) ethynyl) phenyl aldehyde
English language Chemical formula: 2,5-dimethyl-4-((4-(1,2,2-triphenylvinyl) phenyl) ethynyl) benzaldehyde
Synthetic method: similar to the synthetic method of TPE-HPh, difference is to use 4-bromo-2,5-dimethylbenzaldehyde 5 to replace 4-bromo-2,5-bis-hexyloxybenzaldehyde 6; The material added during reaction is 2-(4-ethynyl phenyl)-1,1,2-triphenyl vinyl 4 (1g, 2.81mmol), 4-bromo-2,5-dimethylbenzaldehyde 5 (0.57g, 2.68mmol), two (triphenylphosphine) palladium chloride (II) (0.089g, 0.126mmol), cuprous iodide (0.024g, 0.121mmol) with triphenylphosphine (0.066g, 0.251mmol), obtain product 0.73g, productive rate 70%.MS:488.2；
1H NMR(400MHz,CDCl
3):10.22(s,1H),7.64(s,1H),7.34(s,1H),7.29(s,1H),7.27(s,1H),7.15-7.09(m,9H),7.08-7.01(m,8H),2.61(s,3H),2.50(s,3H)。
(2) TPE-MPh-Bar is synthesized
Chinese chemical name: 5-(2,5-dimethyl-4-((4-(1,2,2-triphenyl vinyl) phenyl) ethynyl) α-tolylene) pyrimidine-2,4,6 (1H, 3H, 5H)-triketone
English language Chemical formula: 5-(2,5-dimethyl-4-((4-(1,2,2-triphenylvinyl) phenyl) ethynyl) benzylidene) pyrimidine-2,4,6 (1H, 3H, 5H)-trione
Synthetic method: similar to the synthetic method of synthesis TPE-HPh-Bar, difference is to use TPE-MPh (370mg, 0.758mmol) and barbituric acid 3 (106mg, 0.828mmol) to obtain product 0.30g, productive rate 65%.HRMS (MALDI-TOF): theoretical value C
41h
30n
2o
3598.2256; Measured value 598.2261;
1h NMR (400MHz, d
6-DMSO) δ 11.55 (s, 1H), 11.32 (s, 1H), 8.45 (s, 1H), 7.62 (s, 1H), 7.49 (s, 1H), 7.44 (d,
2j=8.4Hz, 2H), 7.30-7.22 (m, 9H), 7.13-7.08 (m, 9H), 2.47 (s, 3H), 2.35 (s, 3H);
13c NMR (100MHz, d
6-DMSO) δ 162.90,161.06,152.63,150.28,143.95,142.93,142.91,142.73,141.47,139.84,135.67,135.24,133.64,132.38,131.12,130.90,130.80,130.72,130.69,130.62,128.01,127.96,127.85,126.86,126.78,123.93,120.80,120.27,94.73,88.50,19.77,18.94.
Embodiment 5: TPE-Bar, TPE-s-Bar, TPE-HPh-Bar and TPE-MPh-Bar of preparing embodiment 1-4 comprise the research of the application aspect such as self-assembly micro-nano material, organic optical waveguide, bio-imaging
Carry out purifying to the key intermediates in Fig. 1 and finished product and characterize and then confirm its molecular structure by NMR spectrum and mass spectrum, this luminescent material is dissolved in ordinary organic solvents, comprises THF, methylene dichloride, chloroform and DMSO, water insoluble.
TPE-s-Bar in the mixed solvent of ethanol and chloroform slowly solvent flashing obtain TPE-s-Bar crystal, this crystal is analyzed by X-ray diffraction method.The structure iron (ORTEP) of TPE-s-Bar is see Fig. 2, and the data of crystal are see table 1.
The crystal data of table 2:TPE-s-Bar gathers
As shown in Fig. 3 A, 3B and 3C, three kinds of luminescent materials TPE-s-Bar, TPE-Bar and TPE-MPh-Bar demonstrate obvious aggregation-induced emission (AIE) character in PL spectrum.These compounds are all luminous at more than 550nm, for orange-red light, (be 80vol% for TPE-s-Bar and TPE-Bar after exceeding some water-content values, 70% for TPE-MPh-Bar), along with the continuation of water-content in the mixed solvent of THF/ water increases, luminous intensity sharply rises.And for TPE-HPh-Bar, the phenyl ring replaced due to hexyloxy has larger electronics supply capacity, obvious distortion Intramolecular electron transfer (TICT) process can be observed before AIE.As illustrated in figures 4 a and 4b, TPE-HPh-Bar is at photoluminescence (PL emission) the red shift extremely about 630nm of state of aggregation, compared with being positioned at the TPE-CHO of about 490nm luminescence, owing to introducing electron-withdrawing group barbituric acid, luminous red shift, the preparation of this ruddiness does not need numerous and diverse synthetic work amount.According to integrating sphere technology, the solid state quantum productive rate of TPE-Bar, TPE-s-Bar, TPE-MPh-Bar and TPE-HPh-Bar luminescent material is respectively 19.1%, 20%, 9% and 37.4%.
After using mortar slowly to grind TPE-s-Bar and TPE-Bar, form more red powder, as shown in Figure 5 A and 5B, TPE-s-Bar shows emitting red light (PL) at 567nm, as shown in Figure 6 A and 6B, TPE-Bar shows emitting red light (PL) at 605nm.After fumigating 20min with acetone vapor, come back to initial Yellow luminous, between Yellow luminous and emitting red light, be easy to reversibility conversion.Except stifling, abrasive flour more than 110 DEG C and the TPE-Bar abrasive flour 140 DEG C of heating TPE-s-Bar also can make red powder become crystalline state and the coloured light that turns to be yellow, and display power causes variable color (mechanochromism) behavior.Similarly, TPE-MPh-Bar also shows power and causes variable color (mechanochromism) character, and after grinding, as shown in figs. 7 a-b, luminous maximum change is from 575nm to 600nm.
Causing variable color (mechanochromism) phenomenon to study power, being analyzed by the activation luminophor of powder x-ray diffraction (XRD) to different state of aggregation.As shown in Fig. 8 A and 9A, the XRD diffractogram of primary sample demonstrates many sharp diffraction peak, shows that it is crystalline structure character, and on the contrary, ground sample only shows a large diffuse halo (diffuse halo) therefore for amorphous.When heat-treating red powder or fumigating with acetone vapor, sharp-pointed diffraction peak can occur again, and this shows amorphous powder stifling or thermal treatment and turn back to its crystalline state by solvent.Can be found out by the DSC data of 8B and 9B, the DSC spectrogram of the sample after grinding occur a peak crystallization, this peak crystallization is being formed in the process of crystalline state by unformed shape.Above-mentioned experimental result shows that luminous transformation changes relevant with the topography becoming amorphous state from crystalline state, and vice versa.
The self-assembly of research TPE-HPh-Bar.Drip the acetonitrile solution of several TPE-HPh-Bar on a silicon substrate, naturally volatilize, form the nanometer ball of TPE-HPh-Bar.As shown in Figure 10 A, 10B, 10C and 10D, nanometer ball size is homogeneous, and size is relevant with strength of solution, and strength of solution is higher, and the nanosphere size of formation is larger.Add ethanol or the pattern of water on self-assembly does not affect substantially, but the size of nanometer ball will diminish under same experimental conditions.In order to obtain the homogeneous particle diameter of 500nm, use acetonitrile/ethanol (1:1v/v) mixed solvent, TPE-HPh-Bar concentration is 50 μMs, is 5 times of TPE-HPh-Bar concentration in above-mentioned acetonitrile solution.Are all poor dissolution solvents for second alcohol and water TPE-HPh-Bar, add the gathering that will speed up molecule in these solvents to acetonitrile solution, and then form the nanometer ball of small particle size.
Consider the hydrogen bond action between barbituric acid and trimeric cyanamide, have studied the impact added the nanostructure that TPE-HPh-Bar is formed of trimeric cyanamide, the self-assembly of the TPE-HPh-Bar adding trimeric cyanamide is studied.Because acetonitrile is poor solvent for trimeric cyanamide, only have part TPE-HPh-Bar molecule and melamine molecule to interact, and trimeric cyanamide solvability in DMSO solvent is better, therefore uses DMSO solvent to carry out topography research.First, the DMSO solution of preparation TPE-HPh-Bar, add the appropriate melamine solution being dissolved in DMSO, mixed solution is placed in room temperature lower for some time, then adds ethanol, after adding ethanol, solution drips on a silicon substrate, solvent flashing under unlimited condition, because TPE-HPh-Bar molecular ratio melamine molecule is much bigger, so trimeric cyanamide consumption is relatively high, and then make to be formed between TPE-HPh-Bar molecule and melamine molecule to act on completely.As shown in Figure 11 A and 11B, under the existence of the trimeric cyanamide of 10 equivalents, in the mixed solvent of DMSO/ ethanol (1:1v/v), form the nanotube that length is about 30nm, diameter is about 50nm.The tube end of major part nanotube is ringent, and this may be relevant with DMSO corrosion effect, in the mixture of barbituric acid and trimeric cyanamide, seldom can observe this form.As shown in Figure 11 C and 11D, increase trimeric cyanamide to 25 equivalent, the thickness of nanometer rod has almost no change, but tube end is closed.When the volume ratio of DMSO and ethanol becomes 1:4 from 1:1, micrometer structure and nanostructure can become less and irregular.TPE-HPh-Bar molecule can be assembled in the mixed solvent containing a large amount of ethanol, therefore can hinder the common assembling between itself and melamine molecule.On the other hand, the content reducing DMSO can reduce corrosion effect, and the possibility that ringent nanotube is formed reduces.
Surface does not have TPE-s-Bar and TPE-HPh-Bar micro-nano club shaped structure defective to demonstrate fabulous optical waveguides effect.In order to study the optical waveguides behavior of TPE-s-Bar and TPE-HPh-Bar micron bar further, test photoluminescence (PL) character relevant to distance of TPE-s-Bar with TPE-HPh-Bar micron bar respectively.As shown in Figure 12 A and 13A, the different positions of the wavelength 400nm exciting light produced by the laser apparatus of 800nm to micron bar on the glass sheet excites, and the luminescence of micron bar end is detected, when the position excited moves on to opposite end gradually, luminous intensity dies down, this illustrates that the micron bar of TPE-s-Bar and TPE-HPh-Bar absorbs exciting light in the position excited, and then absorb light is transmitted to the end of micron bar.Optical waveguides behavioural trait is in the phenomenon of end coupling light.
The micron bar of TPE-s-Bar and TPE-HPh-Bar, as organic optical waveguide material, as shown in Figure 12 B, 12C and 13B and 13C, detects the optical loss coefficient of TPE-s-Bar and TPE-HPh-Bar micron bar, record micron bar anchor portion luminous intensity (I
end) and excite the luminous intensity (I of position
body).Optical loss coefficient (α) calculates (I by mono-exponential fit
end/ I
body=Aexp
-α xwherein x represents the distance excited between position and luminous end, A represents the light ratio value and the light ratio value along spread fiber escaped from shot point), the α value of the TPE-s-Bar recorded accordingly is about 0.100dB/ μm and is about 0.130dB/ μm with the α value of TPE-HPh-Bar, shows that two kinds of activation luminophors have fabulous optical waveguides effect.Large Stokes shift (Stokes shift) contributes to the absorption again that TPE-s-Bar and TPE-HPh-Bar overcomes the light escaped from shot point, and this is the principal element of optical loss in communication process.
Same TPE-Bar and TPE-MPh-Bar micron bar is also expected to be used as optical waveguide material.
In biological applications, TPE-HPh-Bar is coated by bovine serum albumin under the assistance of linking agent glutaraldehyde, as shown in figure 14, detect by sweep electron microscope (SEM) and observe, TPE-HPh-Bar after display modification can form homogeneous nanoparticle, in aqueous phase, have good dispersion effect, the particle diameter of this nanoparticle is about 250nm, is easy to by cell internalizing.Therefore the luminescent material of this series is also expected to be applied to imaging technique in cell.
In addition, consider and can be used as the solid luminescent character that such material is good luminescent layer, be expected to for oled device.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, all these improve or conversion all should belong within the protection domain of claims of the present invention.
Claims (10)
1. there is a luminescent material for aggregation-induced emission characteristic, include the group being selected from following arbitrary structural formula:
Wherein, R
1, R
2and R
3be selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, alkoxyl group, aryloxy, carboxyl, lsothiocyanates group, azido-, alkyl diazoimide base, alkylamino, chloro alkyl, bromo alkyl, iodo-alkyl, ester group respectively, R
1, R
2and R
3following structural formula can also be selected from respectively:
or
wherein Y is O, S or Se; R
1and R
2be respectively the alkyl of-H, line style or branching type, R
3and R
4be respectively alkyl or the alkoxyl group of line style or branching type;
In structural formula I and II, respectively at least containing a R
1, R
2or R
3; Y is O, S or Se; R
1and R
2be respectively the alkyl of line style or branching type; R
3and R
4be respectively alkyl or the alkoxyl group of line style or branching type;
Tetraphenyl ethylene unit in structural formula I and II at least comprises one, and is connected by C-C singly-bound, C=C double bond or C ≡ C triple bond.
2. the luminescent material with aggregation-induced emission characteristic according to claim 1, is characterized in that, R
1, R
2and R
3be-H; Y is O.
3. the luminescent material with aggregation-induced emission characteristic according to claim 2, is characterized in that, in structural formula I, and R
1and R
2be selected from-H or alkyl respectively and R
1and R
2it is identical group; In formula II, R
1and R
2be-H, R
3and R
4be selected from alkyl or alkoxyl group respectively and R
3and R
4it is identical group.
4. the luminescent material with aggregation-induced emission characteristic according to claim 3, is characterized in that, in structural formula I, and R
1and R
2be-H or be-CH
3group; In formula II, R
3and R
4be-CH
3or-OC
6h
13group.
5. the application in optical waveguide material prepared by the arbitrary described luminescent material with aggregation-induced emission characteristic of claim 1-4.
6. the application in oled device prepared by the arbitrary described luminescent material with aggregation-induced emission characteristic of claim 1-4.
7. the arbitrary described luminescent material with aggregation-induced emission characteristic of a claim 1-4 is preparing the application of fluorescent dye of imaging in cell.
8. the arbitrary described preparation method with the luminescent material of aggregation-induced emission characteristic of claim 1-4, comprise the steps: as the tetraphenyl ethylene derivative of start material and barbituric acid compounds heating reflux reaction in organic alcohol solvent, form throw out, throw out is filtered, product organic solvent washing after filtration, vacuum-drying obtains luminescent material;
The structural formula of the tetraphenyl ethylene derivative in wherein said start material is:
or
Wherein, R
1, R
2and R
3be selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, alkoxyl group, aryloxy, carboxyl, lsothiocyanates group, azido-, alkyl diazoimide base, alkylamino, chloro alkyl, bromo alkyl, iodo-alkyl, ester group respectively, R
1, R
2and R
3following structural formula can also be selected from respectively:
or
wherein Y is O, S or Se; R
1and R
2be respectively the alkyl of-H, line style or branching type, R
3and R
4be respectively alkyl or the alkoxyl group of line style or branching type;
In the structural formula of the tetraphenyl ethylene derivative in start material, respectively at least containing a R
1, R
2or R
3; Tetraphenyl ethylene unit wherein at least comprises one, and is connected by C-C singly-bound, C=C double bond or C ≡ C triple bond.
9. preparation method according to claim 8, is characterized in that, the barbituric acid compounds in described start material is barbituric acid or N, N-dimethyl barbituric acid; Described organic alcohol solvent is methyl alcohol or ethanol; Described organic solvent is selected from least one in methyl alcohol, ethanol, ether; Described throw out can filtered while hot or be cooled to room temperature and carry out filtration and obtain solid.
10. preparation method according to claim 8, is characterized in that, is also included in the process of heating reflux reaction and adds the step of the vitriol oil as catalyzer; And rear ether and the hexane of using of product washing after filtering is carried out the step of recrystallization to the product filtered.
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