CN104877666B - There is luminescent material of aggregation-induced emission characteristic and its preparation method and application - Google Patents
There is luminescent material of aggregation-induced emission characteristic and its preparation method and application Download PDFInfo
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Abstract
The luminescent material of the present invention has luminous (AIE/AEE) characteristic of aggregation inducing/enhancing, and maximum absorption wavelength red shift is to visibility region, and then such luminescent material has potential application in terms of biology and photoelectric field；There is splendid fiber waveguide property, as little as 0.100dB/ μm of light loss, can be used for preparing optical waveguide material it is also possible to be used for organic light emitting diode device；Such material, due to AIE characteristic, has the characteristics that power mutagens color, and power causes metachromatism reversible, has potential application in terms of intellectual material.
Description
Technical field
The present invention relates to a series of luminous organic materials are and in particular to have aggregation-induced emission or luminescence enhancement (AIE/
AEE) the solid luminescent material of characteristic.
Background technology
With the development of organic optoelectronic, the new organic luminous semiconductor function material using in solid-state or coherent condition
Material, due to compared with traditional inorganic semiconductor material, having that high sensitivity, good device be flexible, inexpensive, little plant bulk,
Large area is prepared and is easy to the advantage such as integrated, and receive more and more attention (Chem.Phys.Lett., 1974,29,
277,Chem.Rev.2007,107,1011).Except organic optoelectronic device, luminous organic material is in information Store
(J.Mater.Chem.C,2013,1,3376；Chem.Soc.Rev.,2013,42,857；Adv.Mater.,2013,25,378；
Chem.Soc.Rev., 2013,42,8895.) and bioscience (Chem.Rev., 2013,113,192；Chem.Sci.,2012,
3,984.) etc. aspect also shows and is widely applied.
However, conventional organic luminescence material is always accompanied by inevitable phenomenon：Assemble to cause and be quenched
(aggregation-caused quenching, ACQ), traditional fluorescent material usually contains larger π-electron conjugated knot
Structure, this structure is mainly for generation of fluorescence.Under molecular melting state, the solution of fluorescent dye shows hyperfluorescence, but dense molten
When liquid status, state of aggregation or solid-state, intermolecular interaction strengthens, and energy transfer occurs, and forms exciplex or excimer,
These all can consume excited energy, therefore greatly reduces the probability of fluorescence radiation, here it is well-known ACQ is existing
As.But in modern technologies application, in most cases, fluorescent material needs to be processed into state of aggregation, and ACQ problem is inevitable.
Have been developed at present various chemistry (Chem.Commun., 2008,1501；Chem.Commun., 2008,217.), physics, with
And engineering method and the course of processing (Langmuir, 2006,22,4799；Macromolecules 2003,36,5285) to weaken
ACQ effect, but these trials are only capable of obtaining less success, main difficulty is that the formation of aggregation is individual in condensed phase
Intrinsic procedure, is therefore badly in need of material and the system that exploitation keeps lighting by force in the collected state.
In calendar year 2001, the research worker of the present invention has synthesized 1,1- dimethyl -2, and 3,4,5- tetraphenyl thiophenes are coughed up (DMTPS) and changed
Compound, its state of aggregation plays beneficial rather than destructive effects (Chem.Commun.2001,1740.) in terms of fluorescence radiation, grinds
Study carefully personnel also to observe a kind of novelty phenomenon and be preced with referred to as " focusing induced luminescence " (aggregation-induced
Emission, AIE), under solution state, non-luminous molecule is formed by aggregation and is induced to light：A series of spiral helicine non-
Light emitting molecule, such as hexaphenyl thiophene coughs up (HPS) and tetraphenyl ethylene (tetraphenylethene, TPE), by formation aggregation
It is induced to send very strong fluorescence (J.Mater.Chem.2001,11,2974；Chem.Commun.2009,4332；
Appl.Phys.Lett.2007,91,011111.), researchers are found that many kinds have the molecule of this characteristic afterwards.Separately
Outward, designed by series of experiments and Theoretical Calculation, researchers confirm that internal molecular motion limited (RIM) is to lead to AIE to be imitated
Main cause (the J.Phys.Chem.B2005,109,10061 answering；J.Am.Chem.Soc.2005,127,6335.).
So far, most of AIE luminous bodys of preparation can only launch blue light and green glow, compared with blue-light emitting material, right
The R and D of the material of gold-tinted and HONGGUANG relatively lag behind, and in organic integrated circuits, gold-tinted and red light material are must not
The assembly that can lack；Similarly for the application of bio-imaging aspect, more preferably those longwave transmissions dye molecule, so will not
By the disturbing of autofluorescence of biological tissue, and excitation source the damage of tissue be will also decrease (Chem.Mater.,
2012,24,812).For the preparation of gold-tinted and green light material, method of the prior art is that the pi-conjugated structure extending molecule is entered
And reduce band gap and be beneficial to electron transition, but this method be disadvantageous in that building-up process is complicated, synthetic work amount big,
Intermolecular interaction strengthens and is quenched, is easily affected by photooxidation and product dissolubility reduces etc. asks thus being easily caused induced luminescence
Topic.
Content of the invention
It is an object of the invention to provide a kind of luminescent material with aggregation-induced emission characteristic and preparation method thereof and should
With solving the problems, such as that the luminescent material with aggregation-induced emission characteristic of the prior art is applied limited.
The present invention solves technical problem and be employed technical scheme comprise that：A kind of luminous material with aggregation-induced emission characteristic
Material, includes the group selected from following any structure formula：
Wherein, R1、R2And R3It is respectively selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl
Base, alkoxyl, aryloxy group, carboxyl, isothiocyanate group, azido, alkyl azide base, alkylamino, chloro alkyl, bromoalkane
Base, iodo-alkyl, ester group, R1、R2And R3Following structural formula can also be respectively selected from：
OrWherein Y is O, S or Se；R1And R2It is respectively the alkyl of-H, line style or branching type, R3And R4Point
Wei not the alkyl of line style or branching type or alkoxyl；
In structure Formulas I and II, at least contain a R respectively1、R2Or R3；Y is O, S or Se；R1And R2Be respectively line style or
The alkyl of branching type；R3And R4The respectively alkyl of line style or branching type or alkoxyl；
Tetraphenyl ethylene unit in structure Formulas I and II at least includes one, and by C -- C single bond, C=C double bond or C ≡
C tri- is bonded.
In the luminescent material with aggregation-induced emission characteristic of the present invention, R1、R2And R3It is-H；Y is O.
In the luminescent material with aggregation-induced emission characteristic of the present invention, in structure Formulas I, R1And R2Be respectively selected from-
H or alkyl and R1And R2It is identical group；In formula II, R1And R2It is-H, R3And R4It is respectively selected from alkyl or alcoxyl
Base and R3And R4It is identical group.
In the luminescent material with aggregation-induced emission characteristic of the present invention, in structure Formulas I, R1And R2Be-H or
It is-CH3Group；In formula II, R3And R4It is-CH3Or-OC6H13Group.
The present invention also provides above-mentioned has the luminescent material of aggregation-induced emission characteristic in preparing optical waveguide material
Application.
The present invention also provides the above-mentioned luminescent material with aggregation-induced emission characteristic preparing Organic Light Emitting Diode
Application in device.
The present invention also provides the above-mentioned luminescent material with aggregation-induced emission characteristic preparing the glimmering of intracellular imaging
The application of light stain.
The present invention also provides the preparation method of the above-mentioned luminescent material with aggregation-induced emission characteristic, walks including following
Suddenly：To be heated to reflux in organic alcohol solvent instead as the tetraphenyl ethylene derivant of start material and barbital acid compounds
Should, form precipitate, precipitate is filtered, the product organic solvent washing after filtration, vacuum drying obtains luminous material
Material；
The structural formula of the tetraphenyl ethylene derivant in wherein said start material is：
Or
Wherein, R1、R2And R3It is respectively selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl
Base, alkoxyl, aryloxy group, carboxyl, isothiocyanate group, azido, alkyl azide base, alkylamino, chloro alkyl, bromoalkane
Base, iodo-alkyl, ester group, R1、R2And R3Following structural formula can also be respectively selected from：
OrWherein Y is O, S or Se；R1And R2It is respectively the alkyl of-H, line style or branching type, R3And R4Point
Wei not the alkyl of line style or branching type or alkoxyl；
In the structural formula of the tetraphenyl ethylene derivant in start material, at least contain a R respectively1、R2Or R3；Its
In tetraphenyl ethylene unit at least include one, and by C -- C single bond, C=C double bond or C ≡ C tri- bonded.
In the preparation process in accordance with the present invention, the barbital acid compounds in described start material are barbituratess or N,
N- dimethyl barbituric acid；Described organic alcohol solvent is methanol or ethanol；Described organic solvent is in methanol, ethanol, ether
At least one；Described precipitate with filtered while hot or can be cooled to room temperature and carries out being filtrated to get solid.
In the preparation process in accordance with the present invention, add concentrated sulphuric acid during being additionally included in heating reflux reaction as catalyst
Step；And the step using ether and hexane, recrystallization being carried out to the product filtering after the product washing after filtering.
It should be noted that described alkyl can be straight chain type or branched chain type, chain contains 1-10 carbon
Atom, preferably contains the alkyl of 2-6 carbon atom；Described cycloalkyl refers to the monocyclic or multi-ring of non-aromatics, containing 3-10 carbon atom；
Described miscellaneous alkyl refers at least one of alkyl carbon atom and is replaced by hetero atom；Heterocyclylalkyl refers in the cycloalkyl of 3-7 ring
At least one ring is hetero atom, and this hetero atom is selected from O, N, S, Si and B；Aryl preferably comprises 6-18 carbon atom, such as phenyl, naphthalene
Base, anthryl, aphthacene group, pyrene group；In aryl containing 5-10 ring, at least one ring is hetero atom, and this is miscellaneous former
Son is selected from O, N, S, Si and B.
Implement luminescent material and its application with aggregation-induced emission characteristic of the present invention, have the advantages that：
The 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, enter
And improve application possibility in terms of biology and optoelectronics for the luminescent material；It is more than 90% THF/H in water content2O mixes
Nanoparticle can be formed, this nanoparticle can enter cell by albumen after coating in solvent；Grinding-stifling and grind-
In heating process, due to molecular conformation crystal and amorphous between change, lead to glow color reversible transition；It is being added without
Nanosphere, nanometer rods and nanotube can be self-assembly of in different solvents under the conditions of tripolycyanamide and addition tripolycyanamide；
There is splendid fiber waveguide property, as little as 0.137dB/ μm of optical loss coefficient, can be used for preparing optical waveguide material；In view of such material
The good solid luminescent property of material is it is also possible to be used for preparing oled device.
Brief description
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 in different water contents (vol%) for the TPE-s-Bar2Luminescence generated by light (PL) spectrum in O solvent
Figure, wherein illustration are the I/I of TPE-s-Bar0And the correlogram between water content, I in system0For TPE-s-Bar pure
Maximum PL intensity in THF, concentration is 10 μM, and excitation wavelength is 420nm；
Fig. 3 B is the THF/H in different water contents (vol%) for the TPE-Bar2Luminescence generated by light (PL) spectrogram in O solvent,
Wherein illustration is the I/I of TPE-Bar0From the correlogram between different water contents, I0Maximum in the pure THF for=TPE-Bar
PL intensity, concentration is 10 μM, and excitation wavelength is 420nm；
Fig. 3 C is the THF/H in different water contents (vol%) for the TPE-MPh-Bar2Luminescence generated by light (PL) spectrum in O solvent
Figure, wherein illustration are the I/I of TPE-MPh-Bar0From the correlogram between different water contents, I0=TPE-MPh-Bar is pure
Maximum PL intensity in THF, concentration is 10 μM, and excitation wavelength is 410nm；
Fig. 4 A is TPE-HPh-Bar in different water content (fw) THF/H2Luminescence generated by light (PL) spectrogram in O solvent,
Wherein concentration is 10 μM, and excitation wavelength is 447nm；
Fig. 4 B is the relative PL intensity I/I of TPE-HPh-Bar0With THF/H2The correlogram of O composition, I0For TPE-
Luminous intensity (emission intensity) in pure THF for the MPh-Bar, illustration is TPE-HPh-Bar in water content difference
THF/H for 0vol% and 95vol%2The fluorescence photo that the solution being formed in O system obtains under ultraviolet light；
Fig. 5 A is the variation diagram of TPE-s-Bar crystal emission spectrum during grinding-solvent is fumigated；
Fig. 5 B is to fumigate, by repeating grinding-solvent, the solid luminescent repetition transition diagram that circulation makes TPE-s-Bar；
Fig. 6 A is the variation diagram of TPE-Bar emission spectrum during grinding-solvent is fumigated；
Fig. 6 B is to fumigate, by repeating grinding-solvent, the repetition transition diagram that circulation makes the solid state fluorescence of TPE-Bar；
Fig. 7 A is the variation diagram of TPE-MPh-Bar emission spectrum during grinding-solvent is fumigated；
Fig. 7 B is to fumigate, by repeating grinding-solvent, the repetition transition diagram that circulation makes the solid state fluorescence of TPE-MPh-Bar；
Fig. 8 A is the heating rate in different coherent condition for the TPE-s-Bar with 10 DEG C of min–1XRD diffraction pattern；
Fig. 8 B is the heating rate in different coherent condition for the TPE-s-Bar with 10 DEG C of min–1DSC thermal analysis curue；
Fig. 9 A is the heating rate in different coherent condition for the TPE-Bar with 10 DEG C of min–1XRD diffraction pattern；
Fig. 9 B is the heating rate in different coherent condition for the TPE-Bar with 10 DEG C of min–1DSC thermal analysis curue；
Figure 10 A be 100 μM of TPE-HPh-Bar solution in acetonitrile by solvent is slow volatilize after the micron ball that formed and
The SEM image of nanosphere；
Figure 10 B is the micron of TPE-HPh-Bar solution formation after the slow volatilization of solvent in acetonitrile of 10 μM of concentration
The SEM image of ball and nanosphere；
Figure 10 C is the TPE-HPh-Bar solution of 50 μM of concentration in acetonitrile/ethanol (1：Pass through molten under room temperature condition in 1v/v)
Agent slowly volatilize formation nanosphere SEM image；
Figure 10 D is the TPE-HPh-Bar solution of 50 μM of concentration in acetonitrile/water (1：Pass through solvent under room temperature condition in 1v/v)
The SEM image of the nanosphere that slow volatilization is formed；
Figure 11 A is that the TPE-HPh-Bar solution of 100 μM of concentration exists under conditions of the tripolycyanamide adding 10 equivalents
(1 in DMSO/ ethanol：The micron ball being formed by solvent slow evaporation under room temperature condition in 1v/v) and the SEM imaging of nanosphere
Figure, scale：5μm；
Figure 11 B is that the TPE-HPh-Bar solution of 100 μM of concentration exists under conditions of adding the tripolycyanamide having 10 equivalents
(1 in DMSO/ ethanol：The micron ball being formed by solvent slow evaporation under room temperature condition in 1v/v) and the SEM imaging of nanosphere
Figure, scale：1μm；
Figure 11 C is that the TPE-HPh-Bar solution of 100 μM of concentration exists under conditions of adding the tripolycyanamide having 25 equivalents
(1 in DMSO/ ethanol：The micron ball being formed by solvent slow evaporation under room temperature condition in 1v/v) and the SEM imaging of nanosphere
Figure, scale：2μm；
Figure 11 D is that the TPE-HPh-Bar solution of 100 μM of concentration exists under conditions of adding the tripolycyanamide having 25 equivalents
(1 in DMSO/ ethanol：Slowly volatilized by solvent under room temperature condition in 1v/v) the SEM imaging of the micron ball of formation and nanosphere
Figure, scale：1μm；
Figure 12 A is to assemble UV laser (400nm) to excite the micro- of the TPE-s-Bar micron bar obtaining in seven diverse locations
Fluorescent images；
Figure 12 B is the micron bar that the right side rod end in 12A, TPE-s-Bar micron bar being recorded is marked with a-g
PL spectrum；
Figure 12 C is TPE-s-Bar peak intensity and the correlogram exciting distance between position and luminous end；
Figure 13 A is to assemble UV laser (400nm) to excite the aobvious of the TPE-HPh-Bar micron bar obtaining in seven diverse locations
Micro- fluorescent images；
Figure 13 B is the micron that the right side rod end in figure 13a TPE-HPh-Bar micron bar being recorded is marked with a-g
The PL spectrum of rod；
Figure 13 C is TPE-HPh-Bar peak intensity and the correlogram exciting distance between position and luminous end；
Figure 14 is the SEM images of the TPE-HPh-Bar nanoparticle encapsulated by bovine serum albumin, scale：1μm.
Specific embodiment
With reference to the accompanying drawings and examples, luminescent material and its application with aggregation-induced emission characteristic to the present invention
It is described further with preparation method：
The concrete preparation process of luminescent material of aggregation-induced emission characteristic that what the present invention was new have is entered by following examples
Row explanation.It should be noted that the luminescent material prepared below is only each structure in the structural formula I-II of protection in claim
One or more of luminescent material represented by formula, but the luminescent material that the present invention is protected is not limited to this.
Wherein embodiment 1-4 building-up process synthetic route shown in Figure 1.
Embodiment 1：Synthesis TPE-Bar
Structural formula：
Chinese chemical name：5- (4- (1,2,2- triphenyl vinyl) benzylidene) 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) benzaldehyde 1 (500mg, 1.39mmol) and barbituratess 3
(186mg, 1.46mmol) mixture flows back 24h in methanol 20mL and THF 5mL mixed solvent, forms bright yellow precipitate,
The bright yellow precipitate being formed is filtered after being cooled to room temperature by reactant mixture, and the solid ethanol after filtration and ether rush respectively
Wash three times, vacuum drying obtains product 390mg, yield is 61%.1H-NMR(400MHz,d6-DMSO):δ11.48(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,d6-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；Elementary analysiss
Theoretical value C31H22N2O3: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) benzylidene) 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) benzaldehyde 1 (500mg, 1.39mmol) and N, N- dimethyl
A concentrated sulphuric acid is added as catalyst, backflow in ethanol (20mL) in barbituratess 2 (227mg, 1.46mmol) mixture
24h, forms orange-yellow precipitate, and the orange-yellow precipitate being formed is filtered, after filtration after being cooled to room temperature by reactant mixture
Solid ethanol and ether flush three times respectively, and vacuum drying obtains product 480mg, and yield is 70%.HR-MS(MALDI-
TOF)C33H26N2O3Theoretical value 498.1943；Measured value:498.1941；1H-NMR(400MHz,CDCl3):δ8.44(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,CDCl3):δ161.72,159.57,157.86,150.27,148.70,142.24,142.12,142.04,
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 includes：(1) synthesize TPE-HPh
Chinese chemical name：2,5- bis- hexyloxy -4- ((4- (1,2,2- triphenyl vinyl) phenyl) acetenyl) benzene first
Aldehyde
English language Chemical formula：2,5-dihexyloxy-4-((4-(1,2,2-triphenylvinyl)phenyl)ethynyl)
benzaldehyde
Synthetic method：Neck round bottom flask adds 2- (4- ethynyl phenyl) -1,1,2- triphenyl vinyl 4 (1g,
2.81mmol), 4- bromo -2,5- two hexyloxybenzaldehyde 6 (1.03g, 2.68mmol), double (triphenylphosphine) palladium chloride (II)
(Pd(PPh3)2Cl2) (0.089g, 0.126mmol), Hydro-Giene (Water Science). (0.024g, 0.121mmol) and triphenylphosphine (0.066g,
0.251mmol), said mixture is carried out with evacuation taken a breath three times with nitrogen simultaneously and then remove oxygen completely, above-mentioned anti-
Answer the triethylamine 10mL of the oxolane 30mL injecting new distillation in flask and no water degasification, back flow reaction 8h under the conditions of 70 DEG C
Form precipitate, after being cooled to room temperature, the precipitate of formation is filtered out, solvent is removed by revolving, will remove after solvent
Residue crosses silicon dioxide chromatography post, with n- hexanes/ch (4：1v/v) carry out eluting and obtain orange/yellow solid shape product
1.3g, yield 73.4%.MS:660.3(M+)；1H NMR(400MHz,CDCl3)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) synthesize TPE-HPh-Bar
Chinese chemical name：5- (2,5- bis- hexyloxy -4- ((4- (1,2,2- triphenyl vinyl) phenyl) acetenyl) benzene
Methylene) 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：Round-bottomed flask adds TPE-HPh (500mg, 0.758mmol) and barbituratess 3 (106mg,
0.828mmol), it is subsequently adding methanol 40mL and THF 5mL, said mixture is stirred in nitrogen atmosphere and is heated to reflux
24h, forms red precipitate, filtered while hot, the filtration product methanol obtaining flushes three times, then by the red solid obtaining
It is dissolved in ether, add appropriate hexane, be then recrystallized to give crystalline product 0.356g, yield 61%.1H NMR
(400MHz,CDCl3),δ9.06(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,CDCl3),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)C51H50N2O5Theoretical value 770.3720；Measured value 770.3722. Elemental Analysis theory C51H50N2O5: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 includes：(1) synthesize TPE-MPh
Chinese chemical name：2,5- dimethyl -4- ((4- (1,2,2- triphenyl vinyl) phenyl) acetenyl) benzaldehyde
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 using 4- bromo -2,5- dimethyl benzene
Formaldehyde 5 replaces 4- bromo -2,5- two hexyloxybenzaldehyde 6；The material adding 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), double (triphenyl
Phosphine) palladium chloride (II) (0.089g, 0.126mmol), Hydro-Giene (Water Science). (0.024g, 0.121mmol) and triphenylphosphine
(0.066g, 0.251mmol), obtains product 0.73g, yield 70%.MS:488.2；1H NMR(400MHz,CDCl3):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) synthesize TPE-MPh-Bar
Chinese chemical name：(2,5- dimethyl -4- ((4- (1,2,2- triphenyl vinyl) phenyl) acetenyl) benzene is sub- for 5-
Methyl) 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 barbituratess 3 (106mg, 0.828mmol) obtain product 0.30g, yield 65%.HRMS
(MALDI-TOF):Theoretical value C41H30N2O3598.2256；Measured value 598.2261；1H NMR(400MHz,d6-DMSO)δ11.55
(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,d6-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 embodiment 1-4 preparation is entered
Row includes the research of the application aspect such as self assembly micro-nano material, organic optical waveguide, bio-imaging
Key intermediates in Fig. 1 and finished product are carried out with purification and characterized by NMR spectra and mass spectrum and then
Confirm its molecular structure, this luminescent material is dissolved in ordinary organic solvents, including THF, dichloromethane, chloroform and DMSO, do not dissolve in
Water.
TPE-s-Bar slow solvent flashing in the mixed solvent of ethanol and chloroform obtains TPE-s-Bar crystal, this crystal
It is analyzed by X-ray diffraction method., referring to Fig. 2, the data of crystal is referring to table 1 for the structure chart (ORTEP) of TPE-s-Bar.
Table 2：The crystal data of TPE-s-Bar collects
As shown in Fig. 3 A, 3B and 3C, three kinds of luminescent materials TPE-s-Bar, TPE-Bar and TPE-MPh-Bar are in PL spectrum
In show obvious aggregation-induced emission (AIE) property.These compounds all light in more than 550nm, are orange-red light, surpass
After crossing some water content value (being 80vol% for TPE-s-Bar and TPE-Bar, be 70% for TPE-MPh-Bar), with
The continuation water content in the mixed solvent of THF/ water increases, and luminous intensity steeply rises.And for TPE-HPh-Bar, due to
The phenyl ring that hexyloxy replaces has larger electronics supply capacity, it is observed that significantly distorting intramolecular charge before AIE
Transfer (TICT) process.As illustrated in figures 4 a and 4b, TPE-HPh-Bar is red in the luminescence generated by light (PL emission) of coherent condition
Move to about 630nm, compared with being located at the TPE-CHO that about 490nm lights, due to introducing electron withdraw group barbituratess, light red
Move, the preparation of this HONGGUANG does not need numerous and diverse synthetic work amount.According to integrating sphere technology, TPE-Bar, TPE-s-Bar, TPE-
The solid state quantum yield of MPh-Bar and TPE-HPh-Bar luminescent material is respectively 19.1%, 20%, 9% and 37.4%.
Slowly ground after TPE-s-Bar and TPE-Bar using mortar, form more red powder, as shown in Figure 5 A and 5B,
In 567nm display emitting red light (PL), as shown in Figure 6 A and 6B, TPE-Bar shows emitting red light in 605nm to TPE-s-Bar
(PL).Fumigated after 20min with acetone vapor, come back to initial Yellow luminous, Yellow luminous hold very much and emitting red light between
Easily reversibility conversion.In addition to stifling, heat more than 110 DEG C of abrasive flour and the TPE-Bar abrasive flour 140 of TPE-s-Bar
DEG C also red powder can be made to be changed into crystalline state and the coloured light that turns to be yellow, show power mutagens color (mechanochromism) behavior.Similar
Ground, TPE-MPh-Bar displays that power mutagens color (mechanochromism) property, after grinding, as shown in figs. 7 a-b, lights
Maximum change is from 575nm to 600nm.
In order to study power mutagens color (mechanochromism) phenomenon, by powder x-ray diffraction (XRD) to different poly-
The activation luminophor of collection state is analyzed.As shown in Fig. 8 A and 9A, the XRD diffraction pattern of primary sample shows many points
Sharp diffraction maximum, shows that it is crystalline structure property, on the contrary, ground sample only shows that a big diffusion is swooned (diffuse
Halo it is) therefore amorphous.When red powder being carried out with heat treatment or is fumigated with acetone vapor, sharp diffraction maximum can be again
Secondary appearance, this show amorphous powder by solvent fumigate or heat treatment and return to its crystalline state.By the DSC of 8B and 9B
Data can be seen that and occurs in that a peak crystallization on the DSC spectrogram of the sample after grinding, this peak crystallization be from unformed shape to
Crystalline state is formed during changing.Above-mentioned test result indicate that the luminous topography changing and being changed into amorphous state from crystalline state
Change relevant, vice versa.
The self assembly of research TPE-HPh-Bar.Drip the acetonitrile solution of several TPE-HPh-Bar on a silicon substrate, naturally wave
Send out, form the nanosphere of TPE-HPh-Bar.As shown in Figure 10 A, 10B, 10C and 10D, nanosphere size is homogeneous, and size with
Solution concentration is relevant, and solution concentration is higher, and the nanosphere size of formation is bigger.Add ethanol or water basic to the pattern of self assembly
Do not affect, but the size of nanosphere will diminish under same experimental conditions.The particle diameter homogeneous in order to obtain 500nm, uses
Acetonitrile/ethanol (1：1v/v) mixed solvent, TPE-HPh-Bar concentration is 50 μM, is that in above-mentioned acetonitrile solution, TPE-HPh-Bar is dense
5 times of degree.For TPE-HPh-Bar, second alcohol and water is all poor dissolution solvent, adds these solvents to acetonitrile solution
The middle gathering by acceleration molecular, and then form the nanosphere of small particle.
In view of the hydrogen bond action between barbituratess and tripolycyanamide, the addition that have studied tripolycyanamide is to TPE-HPh-
The impact of the nanostructured that Bar is formed, the self assembly to the TPE-HPh-Bar adding tripolycyanamide is studied.Due to acetonitrile
It is poor solvent for tripolycyanamide, only part TPE-HPh-Bar molecule and melamine molecule interact, and three
Poly cyanamid dissolubility in DMSO solvent preferably, therefore carries out topography research using DMSO solvent.First, prepare TPE-HPh-
The DMSO solution of Bar, adds the appropriate melamine solution being dissolved in DMSO, mixed solution is placed in next section of room temperature
Time, it is subsequently adding ethanol, after adding ethanol, solution drips on a silicon substrate, and solvent flashing under the conditions of opening wide, due to TPE-
HPh-Bar molecular proportion melamine molecule is much bigger, so tripolycyanamide consumption is of a relatively high, and then so that TPE-HPh-Bar is divided
Formed between son and melamine molecule and act on completely.As shown in Figure 11 A and 11B, in the presence of the tripolycyanamide of 10 equivalents,
In DMSO/ ethanol (1:Form length about 30nm, the nanotube of diameter about 50nm in mixed solvent 1v/v).Most of nanotube
Tube end be ringent, this may be relevant with DMSO corrosion effect, in the complex of barbituratess and tripolycyanamide very
I haven't seen you for ages observes this form.As shown in Figure 11 C and 11D, increase tripolycyanamide to 25 equivalents, the thickness of nanometer rods does not almost have
Change, but tube end is in closed.When the volume ratio of DMSO and ethanol is from 1：1 is changed into 1：4, micrometer structure and nanostructured
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 itself common assembling and melamine molecule between.On the other hand, the content reducing DMSO can reduce corrosion effect, opening
The probability that the nanotube of shape is formed reduces.
Surface does not have TPE-s-Bar and TPE-HPh-Bar micro-nano club shaped structure defective to show fabulous fiber waveguide effect
Should.In order to study the fiber waveguide behavior of TPE-s-Bar and TPE-HPh-Bar micron bar further, test TPE-s-Bar respectively
Luminescence generated by light (PL) property related to distance with TPE-HPh-Bar micron bar.As shown in Figure 12 A and 13A, by 800nm's
The wavelength 400nm exciting light that laser instrument produces excites to the diverse location of micron bar on the glass sheet, and to micron bar end
The luminous of portion is detected, when the position exciting is gradually moved to opposite end, luminous intensity dies down, this explanation TPE-s-Bar and
The micron bar of TPE-HPh-Bar absorbs exciting light in the position exciting, and then absorbing light propagates to the end of micron bar.At end
The phenomenon that portion couples light is fiber waveguide behavioural trait.
The micron bar of TPE-s-Bar and TPE-HPh-Bar as organic optical waveguide material, such as Figure 12 B, 12C and 13B
With shown in 13C, detect the optical loss coefficient of TPE-s-Bar and TPE-HPh-Bar micron bar, record micron bar anchor portion and light
Intensity (Iend) and excite the luminous intensity (I of positionbody).Optical loss coefficient (α) calculates (I by mono-exponential fitend/Ibody=
Aexp-αx, wherein x represents and excites the distance between position and luminous end, A represent the light ratio escaped from shot point with along optical fiber
The light ratio propagated), the α value of the TPE-s-Bar recording accordingly is about the 0.100dB/ μm of α value with TPE-HPh-Bar and is about
0.130dB/ μm, show that two kinds of activation luminophors have fabulous fiber waveguide effect.Big Stokes shift (Stokes
Shift) contribute to the absorption again that TPE-s-Bar and TPE-HPh-Bar overcomes the light escaped from shot point, this is to be propagated through
The principal element of light loss in journey.
Same TPE-Bar and TPE-MPh-Bar micron bar is also expected to as optical waveguide material.
In biological applications, TPE-HPh-Bar is coated by bovine serum albumin under the assistance of cross-linking agent glutaraldehyde, such as
Shown in Figure 14, detect and observe by sweep electron microscope (SEM), the TPE-HPh-Bar after display is modified can be formed
Homogeneous nanoparticle, has preferable dispersion effect in aqueous phase, and the particle diameter about 250nm of this nanoparticle is it is easy to by cell internalizing.
Therefore this serial luminescent material is also expected to be applied to intracellular imaging technique.
In addition, it is contemplated that the good solid luminescent property of such material, organic light emission two can be expected to be used for as luminescent layer
Pole pipe device.
It should be appreciated that for those of ordinary skills, can be improved according to the above description or be converted,
All these improvement or conversion all should belong within the protection domain of claims of the present invention.
Claims (10)
1. a kind of luminescent material with aggregation-induced emission characteristic, its structural formula is as follows：
Wherein, R1、R2And R3It is respectively selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, alkane
Epoxide, aryloxy group, carboxyl, isothiocyanate group, azido, alkyl azide base, alkylamino, chloro alkyl, bromo alkyl, iodine
Substituted alkyl, ester group, R1、R2And R3Following structural formula can also be respectively selected from：
Wherein Y is O, S or Se；R1And R2It is respectively the alkyl of-H, line style or branching type, R3And R4Point
Wei not the alkyl of line style or branching type or alkoxyl.
2. the luminescent material with aggregation-induced emission characteristic according to claim 1 is it is characterised in that R1、R2And R3All
For-H；Y is O.
3. the luminescent material with aggregation-induced emission characteristic according to claim 2 is it is characterised in that in structure Formulas I
In, R1And R2It is respectively selected from-H or alkyl and R1And R2It is identical group.
4. the luminescent material with aggregation-induced emission characteristic according to claim 3 is it is characterised in that in structure Formulas I
In, R1And R2It is-H or be-CH3Group.
5. optical waveguide material prepared by a kind of arbitrary described luminescent material with aggregation-induced emission characteristic of claim 1-4
In application.
6. organic light emission two prepared by a kind of arbitrary described luminescent material with aggregation-induced emission characteristic of claim 1-4
Application in pole pipe device.
7. intracellular imaging prepared by a kind of arbitrary described luminescent material with aggregation-induced emission characteristic of claim 1-4
Fluorescent dye application.
8. the preparation method of the arbitrary described luminescent material with aggregation-induced emission characteristic of a kind of claim 1-4, including
Following steps：To heat in organic alcohol solvent as the tetraphenyl ethylene derivant of start material and barbital acid compounds
Back flow reaction, forms precipitate, precipitate is filtered, the product organic solvent washing after filtration, vacuum drying obtains
Luminescent material；
The structural formula of the tetraphenyl ethylene derivant in wherein said start material is：
Wherein, R1、R2And R3It is respectively selected from the alkyl of-H, line style or branching type, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, alkane
Epoxide, aryloxy group, carboxyl, isothiocyanate group, azido, alkyl azide base, alkylamino, chloro alkyl, bromo alkyl, iodine
Substituted alkyl, ester group, R1、R2And R3Following structural formula can also be respectively selected from：
Wherein Y is O, S or Se；R1And R2It is respectively the alkyl of-H, line style or branching type, R3And R4Point
Wei not the alkyl of line style or branching type or alkoxyl.
9. preparation method according to claim 8 is it is characterised in that barbital acids chemical combination in described start material
Thing is barbituratess or N, N- dimethyl barbituric acid；Described organic alcohol solvent is methanol or ethanol；Described organic solvent is selected from
At least one in methanol, ethanol, ether；Described precipitate can with filtered while hot or be cooled to room temperature carry out being filtrated to get solid
Body.
10. preparation method according to claim 8 is it is characterised in that add during being additionally included in heating reflux reaction
Enter concentrated sulphuric acid as the step of catalyst；And using ether and hexane, the product filtering is entered after the product washing after filtering
The step of row recrystallization.
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