CN101768138A - Organic micro-molecular film containing protonized nitrogen atoms and preparation method thereof - Google Patents

Organic micro-molecular film containing protonized nitrogen atoms and preparation method thereof Download PDF

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CN101768138A
CN101768138A CN201010300069A CN201010300069A CN101768138A CN 101768138 A CN101768138 A CN 101768138A CN 201010300069 A CN201010300069 A CN 201010300069A CN 201010300069 A CN201010300069 A CN 201010300069A CN 101768138 A CN101768138 A CN 101768138A
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organic molecule
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protonated nitrogen
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atoms
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朱园园
薛敏钊
钱凌峰
马宁
盛巧荣
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Shanghai Jiaotong University
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Abstract

The invention provides an organic micro-molecular film containing protonized nitrogen atoms and a preparation method thereof, belonging to the technical field of organic photoelectric materials. The structural formulae of the organic micro-molecular film are shown in the following figure, wherein R1, R2, R3 and R4 represent any structural formula selected from four structural formulae as shown in the following figure. The organic micro-molecular film prepared by the preparation method using the constant-potential or constant-current electrodeposition method has a uniform surface and consists of nano-particles or lamellar crystal without oxidation products; the shape and thickness of the organic micro-molecular film can be controlled by regulating the electrolyte concentration, working voltage, working current and deposition time; and meanwhile, the preparation method of the invention has the advantages of low energy consumption, easily controllable operation and low cost, so the invention is suitable for industrialized production.

Description

Contain organic molecule film that can protonated nitrogen-atoms and preparation method thereof
Technical field
What the present invention relates to is product of a kind of photoelectric material technical field and preparation method thereof, specifically be a kind of contain can protonated nitrogen-atoms organic molecule film and preparation method thereof.
Background technology
It is big or small to regulate molecular energy system that nitrogenous aromatic heterocycle often is introduced into the conjugated molecule with photoelectric properties, improves charge-conduction, optical physics and the spectrochemical property of molecule.Conjugated molecule with nitrogenous aromatic heterocycle is widely used in fields such as field-effect transistor, photodiode, solar cell, all needs to make the film of photoelectric properties excellence in the application in these fields.The traditional method for preparing this type of molecular film is vacuum evaporation, as the preparation method of the organic electroluminescent device of disclosed use nitogen-contained heterocycle derivant among the CN101410380.Though vacuum evaporation can obtain high performance photoelectric device, this method steps is loaded down with trivial details, should not operate, and the cost height, be subjected to certain limitation in the scale operation field.Other one preparation method commonly used of film is a solution method, as disclosed in the Japanese kokai publication sho 57-51781 communique, material dissolution behind solvent, is adopted spin-coating method to obtain film, but requires compound to have good solubility and film-forming properties.Have the molecule of nitrogenous aromatic heterocycle because the rigidity of molecular structure is poorly soluble, and easy crystallization, be difficult to obtain the careful uniform film of pattern with solution method.
Electrochemical deposition has been widely used in preparing the inorganics film of various patterns as a kind of cost method low, simple to operate.Find through retrieval prior art, be electrochemically-deposited in the preparation field of organic thin film, mainly show following two aspects: (1) is at as phthalocyanine, the organic molecule that this type of chemical property of porphyrin is stable, at first utilize protonating agent to make it protonated, again according to electrophoretic mechanism, adopt the constant potential galvanic deposit to obtain film, as Sun Jingzhi etc. in " electrochemical deposition porphyrin-perylene diimide molecular array film " (Science Bulletin 2005,17,1450-1453) and Hiroaki Yamanouchi etc. at " electrophoretic deposition of CuPc in trifluoroacetic acid-methylene dichloride mixed solution " (Chemistry Letters 2000,1,10-11) described in the article; (2) at the organic molecule that contains just like reactive groups such as thiophene, pyrroles, aniline, utilize the mechanism of electropolymerization, obtain polymeric film in anode generation oxypolymerization, (Macromolecules 2007 described in " by a kind of synthetic a kind of novel electrochromic polymer of electropolymerization of the new bipolar molecule of electron donor-acceptor (EDA) " article as Jose Natera etc., 40,4456-4463).But the polymeric film that the prior art but only limits to prepare the stable organic molecule film of chemical property and contains reactive group does not find that by retrieval similar techniques is applied to the bibliographical information of this area.
Summary of the invention
The present invention is directed to the prior art above shortcomings, provide a kind of contain can protonated nitrogen-atoms organic molecule film and preparation method thereof, the organic molecule film surface that utilizes the method for constant potential or continuous current galvanic deposit to prepare is even, its pattern and thickness can be by regulating concentration of electrolyte, operating voltage, working current and depositing time control, it is little that the while preparation method has energy consumption, behaviour does easy control, and the advantage that cost is low is suitable for suitability for industrialized production.
The present invention is achieved by the following technical solutions:
The present invention utilizes the unsaturated nitrogen atom on the nitrogenous aromatic heterocycle to have in conjunction with the proton ability; make its protonated positively charged ion that obtains having electrophoresis behavior by adding protonic acid; again by galvanic deposit, negative electrode obtain careful evenly, have nano particle or tabular crystal pattern film.By 1H NMR, the test of FT-IR determines that thin film composition is a raw molecule; By test, determine the protonation reaction that proposes among the present invention to solution UV-vis absorption spectrum; By test, characterized the photophysical property and the electrochemical properties of the film of the present invention's preparation respectively to film UV-vis absorption spectrum and cyclic voltammetric; By the test of SEM and XRD, characterized the surface topography and the crystal structure characteristic of the film of the present invention's preparation respectively.
The present invention relates to contain can protonated nitrogen-atoms the organic molecule film, its structural formula is:
Wherein: the structural formula of R1, R2, R3, R4 is respectively any one in following four kinds:
Figure G201010300069820100107D000022
The present invention relates to the above-mentioned preparation method who contains organic molecule film that can protonated nitrogen-atoms, may further comprise the steps:
The first step, will contain can protonated nitrogen-atoms organic molecule be dissolved or dispersed in the reaction vessels that fills organic solvent, it is 10 that configuration obtains concentration -6Mol/L～10 -1The organic solution of mol/L;
Described organic solvent is N, dinethylformamide, CHCl 3, CH 3CN or CH 3NO 2In a kind of or its combination.
Second step, in reaction vessels, add protonic acid after ultra-sonic dispersion or mechanical stirring obtain electrolytic solution;
The content that described protonic acid accounts for the TBT mixed solution is 10 -5Mol/L～10mol/L, this protonic acid are a kind of or its combination in trifluoroacetic acid, thin acid or the hydrochloric acid.
The 3rd step, being anodal with the platinum electrode, is negative pole with conductive metal sheet or conductive glass, and positive pole and negative pole are placed electrolytic solution, applies voltage and carries out electrodeposition process, obtains deposit film;
The spacing of described positive pole and negative pole is set to 5mm～35mm,
Described positive pole and negative pole adopt washing composition, deionized water, acetone, isopropyl acetone and ethanol to carry out ultrasonic cleaning after vacuum drying treatment 1～4h before carrying out electrodeposition process successively.
The described voltage that applies is meant: on anodal and negative pole, apply voltage difference respectively and be-0.2V～-operating voltage of 5V;
Described electrodeposition process is meant: be provided with working current for-0.02mA～-3mA, electrolyte temperature are 10 ℃～50 ℃, depositing time is 0.5min～5min.
The 4th step, with deposit film place encloses container obtain after drying containing can protonated nitrogen-atoms the organic molecule film.
Described drying is meant: carry out the seasoning of 2～10h earlier, then at 50 ℃～100 ℃ following vacuum-drying 2～10h.
The method for manufacturing thin film that the present invention proposes, its advantage has been to utilize the unsaturated nitrogen atom on the nitrogenous hydridization to have ability in conjunction with proton, use protonic acid to make it that protonation reaction take place, obtaining under electric field can electrophoretic protonated product, thereby can use simple electro-deposition method and obtain the organic molecule film, avoid the Vacuum Coating method of traditional complexity.In addition, the voltage that galvanic deposit is used among the present invention is low, and electric current is little, makes the organic molecule that contains reactive group not oxidized at anode, and can obtain the small molecules film at negative electrode.Preparation time of the present invention is short, and simple to operate, old low, and the pattern of film and thickness can be regulated according to concentration of electrolyte, operating voltage, working current and depositing time, and the film of preparation is careful evenly.The present invention can be applicable to the preparation field of photoelectric device.
Description of drawings
Fig. 1 is the absorption spectrum comparison diagram of embodiment 3.
Fig. 2 is the absorption spectrum synoptic diagram of embodiment 8.
Fig. 3 is the SEM figure of embodiment 7.
Fig. 4 is the SEM figure of embodiment 8.
Fig. 5 is the XRD figure of embodiment 8.
Fig. 6 is the cyclic voltammetry curve of embodiment 10
Fig. 7 is a raw material 4,7-two-triphen amido-benzo-2,1,1H NMR (CDCl3) phenogram of 3-thiadiazoles.
Fig. 8 is 1H NMR (CDCl3) phenogram of embodiment 8.
Fig. 9 is that the IR (KBr sheet) of embodiment 8 characterizes comparison diagram.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
With 4,7-two-triphen amido-benzo-2,1,3-thiadiazoles and CH 3CN is with 10 -5Mol: the mixed of 1 L adds 10 -3Mol: the trifluoroacetic acid of 1 L amount, with the ultrasonic 20min of this mixed solution; Positive and negative electrode is placed this system, is anodal with the platinum electrode, is negative pole with the conductive glass, and the positive and negative electrode spacing is 10mm, and uses washing composition, deionized water, acetone, isopropyl acetone, ethanol ultrasonic cleaning successively, vacuum-drying 1h before using; Method with constant potential is carried out galvanic deposit, and operating voltage is 1.0V, at room temperature (25 ℃) deposition 2min; The conductive glass that deposits film is taken out, placed encloses container seasoning 5h, then at 80 ℃, dry 5h under the vacuum, preparation work is finished.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000041
Molecular formula is C 42H 30N 4S, molecular weight are 622.78.
Embodiment 2
Identical with embodiment 1, but with solvent C H 3CN is changed to CH 3NO 2
Embodiment 2 is identical with embodiment 1, but with 4,7-two-triphen amido-benzo-2,1,3-thiadiazoles and CH 3The ratio of CN becomes 10 -3: 1
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 3
Identical with embodiment 1, but with solvent C H 3CN is changed to CH 3NO 2
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 4
Identical with embodiment 3, but 4,7-two-triphen amido-benzo-2,1,3-thiadiazoles and CH 3NO 2The ratio of getting becomes 10 -3: 1.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 5
Identical with embodiment 4, but trifluoroacetic acid and CH 3NO 2Ratio become TBT and CH 3NO 2Ratio become 10 -4: 1.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 6
Same with embodiment 4 machines, but trifluoroacetic acid and CH 3NO 2Ratio become 10 -2: 1.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 7
Identical with embodiment 4, but trifluoroacetic acid and CH 3NO 2Ratio become 10 -1: 1.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 8
Identical with embodiment 6, but operating voltage becomes-0.4V.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 9
Identical with embodiment 7, but operating voltage becomes-2V.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 10
Identical with embodiment 8, but depositing time becomes 5min.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 11
Identical with embodiment 8, but electrolyte temperature becomes 40 ℃.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 12
Identical with embodiment 8, but adopt the continuous current galvanic deposit, working current is-0.06mA.
Present embodiment prepares the structural formula of the organic molecule film that containing of gained can protonated nitrogen-atoms with embodiment 1.
Embodiment 13
Identical with embodiment 1, but with 4,7-two-triphen amido-benzo-2,1, the 3-thiadiazoles is changed to 4,7-two-hexichol amido-benzo-2,1,3-thiadiazoles.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000051
Molecular formula is C 30H 22N 4S, molecular weight are 470.59.
Embodiment 14
Identical with embodiment 2, but with 4,7-two-triphen amido-benzo-2,1, the 3-thiadiazoles is changed to 4,7-two-phenyl-benzo-2,1,3-thiadiazoles.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000052
Molecular formula is C 18H 12N 2S, molecular weight are 288.37.
Embodiment 15
Identical with embodiment 3, but with 4,7-two-triphen amido-benzo-2,1, the 3-thiadiazoles is changed to 4,7-two-thienyl-benzo-2,1,3-thiadiazoles.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000053
Molecular formula is C 14H 8N 2S 3, molecular weight is 300.42.
Embodiment 16
Identical with embodiment 4, but with 4,7-two-triphen amido-benzo-2,1, the 3-thiadiazoles is changed to 4,7-two-triphen amido-benzo-2,1,3-oxygen diazole.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Molecular formula is C 42H 30N 4O, molecular weight are 600.71.
Embodiment 17
Identical with embodiment 16, but with 4,7-two-triphen amido-benzo-2,1,3-oxygen diazole is changed to 4,7-two-phenyl-benzo-2,1,3-oxygen diazole.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000062
Molecular formula is C 18H 12N 2O, molecular weight are 272.30.
Embodiment 18
Identical with embodiment 16, but with 4,7-two-triphen amido-benzo-2,1,3-oxygen diazole is changed to 4,7-two-thienyl-benzo-2,1,3-oxygen diazole.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000063
Molecular formula is C 14H 8N 2OS 2, molecular weight is 284.36.
Embodiment 19
Identical with embodiment 7, but with 4,7-two-triphen amido-benzo-2,1, the 3-thiadiazoles is changed to 5,8-two-phenyl-quinoline.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Molecular formula is C 21H 17N, molecular weight are 283.37.
Embodiment 20
Identical with embodiment 19, but with 5,8-two-phenyl-quinoline is changed to 5,6,7,8-four-phenyl-quinoline.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Molecular formula is C 33H 25N, molecular weight are 435.56.
Embodiment 21
Identical with embodiment 7, but with 4,7-two-triphen amido-benzo-2,1, the 3-thiadiazoles is changed to 5,8-two-triphen amido-quinoxaline.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Molecular formula is C 44H 34N 4, molecular weight is 618.77.
Embodiment 22
Identical with embodiment 21, but with 5,8-two-triphen amido-quinoxaline is changed to 5,8-two-phenyl-quinoxaline.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000072
Molecular formula is C 20H 16N 2, molecular weight is 284.35.
Embodiment 23
Identical with embodiment 21, but with 5,8-two-triphen amido-quinoxaline is changed to 5,8-two-thienyl-quinoxaline.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000073
Molecular formula is C 16H 12N 2S 2, molecular weight is 296.41.
Embodiment 24
Identical with embodiment 21, but with 5,8-two-triphen amido-quinoxaline is changed to 6,7-two-triphen amido-quinoxaline.
The structural formula that present embodiment prepares the organic molecule film that containing of gained can protonated nitrogen-atoms is:
Figure G201010300069820100107D000074
Molecular formula is C 44H 34N 4, molecular weight is 618.77.
The various embodiments described above prepared contain can protonated nitrogen-atoms the organic molecule film, film surface is even, can be by changing the film that electrodeposition condition obtain nano particle and tabular crystal pattern respectively, and its composition is raw material, do not have oxidation products.The present embodiment preparation of organic micromolecule film for this reason provides a kind of method of simple possible, is easy to suitability for industrialized production.The film of present embodiment preparation can be applicable to field of photovoltaic materials such as light emitting diode, solar cell, field-effect transistor.

Claims (9)

  1. One kind contain can protonated nitrogen-atoms the organic molecule film, it is characterized in that its structural formula is:
    Figure F201010300069820100107C000011
    Wherein the structural formula of RR2, R3, R4 is respectively any one in following four kinds:
    Figure F201010300069820100107C000012
  2. 2. a preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 1 is characterized in that, may further comprise the steps:
    The first step, will contain can protonated nitrogen-atoms organic molecule be dissolved or dispersed in the reaction vessels that fills organic solvent, it is 10 that configuration obtains concentration -6Mo l/L～10 -1The organic solution of mo l/L;
    Second step, in reaction vessels, add protonic acid after ultra-sonic dispersion or mechanical stirring obtain electrolytic solution;
    The 3rd step, being anodal with the platinum electrode, is negative pole with conductive metal sheet or conductive glass, and positive pole and negative pole are placed electrolytic solution, applies voltage and carries out electrodeposition process, obtains deposit film;
    The 4th step, with deposit film place encloses container obtain after drying containing can protonated nitrogen-atoms the organic molecule film.
  3. 3. the preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 2 is characterized in that described organic solvent is N, a kind of or its combination among dinethylformamide, CHCl3, CH3CN or the CH3NO2.
  4. 4. the preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 2, it is characterized in that, the content that described protonic acid occupies machine small molecules mixed solution is 10-5mol/L～10mol/L, and this protonic acid is a kind of or its combination in trifluoroacetic acid, sulfuric acid or the hydrochloric acid.
  5. 5. the preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 2 is characterized in that the spacing of described positive pole and negative pole is set to 5mm～35mm.
  6. 6. the preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 2, it is characterized in that described positive pole and negative pole adopt washing composition, deionized water, acetone, isopropyl acetone and ethanol to carry out ultrasonic cleaning after vacuum drying treatment 1～4h successively before carrying out electrodeposition process.
  7. 7. the preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 2 is characterized in that the described voltage that applies is meant: on anodal and negative pole, apply voltage difference respectively and be-0.2V～-operating voltage of 5V.
  8. 8. the preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 2, it is characterized in that, described electrodeposition process is meant: be provided with working current for-0.02mA～-3mA, electrolyte temperature are 10 ℃～50 ℃, depositing time is 0.5min～5min.
  9. 9. the preparation method who contains organic molecule film that can protonated nitrogen-atoms according to claim 2 is characterized in that described drying is meant: carry out the seasoning of 2～10h earlier, then at 50 ℃～100 ℃ following vacuum-drying 2～10h.
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US9287419B2 (en) 2011-01-05 2016-03-15 Nitto Denko Corporation Wavelength conversion perylene diester chromophores and luminescent films
US9382424B2 (en) 2011-09-26 2016-07-05 Nitto Denko Corporation Highly-fluorescent and photo-stable chromophores for enhanced solar harvesting efficiency
US9394479B2 (en) 2011-10-05 2016-07-19 Nitto Denko Corporation Wavelength conversion film having pressure sensitive adhesive layer to enhance solar harvesting efficiency
CN110386930A (en) * 2018-04-18 2019-10-29 香港科技大学 Aggregation-induced emission compound, preparation method and its application

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