CN103013498B - Application of 2,7-di(triphenylamine diamine) spirobifluorene - Google Patents
Application of 2,7-di(triphenylamine diamine) spirobifluorene Download PDFInfo
- Publication number
- CN103013498B CN103013498B CN201210591635.4A CN201210591635A CN103013498B CN 103013498 B CN103013498 B CN 103013498B CN 201210591635 A CN201210591635 A CN 201210591635A CN 103013498 B CN103013498 B CN 103013498B
- Authority
- CN
- China
- Prior art keywords
- triphenylamine
- spirobifluorene
- diamine
- spiral shell
- fluorenes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention belongs to the field of material science, and in particular relates to application of spirobifluorene compounds 2,7-di(triphenylamine diamine) spirobifluorene to the preparation of an organic two-photon absorption material and a two-photon induced blue fluorescent material. Results of various performance tests indicate that 2,7-di(triphenylamine diamine) spirobifluorene provided by the invention can be used as an organic two-photon absorption material, has the advantages of high nonlinearity, heat stability, better transparency and the like, and can be applied to the fields of a full-light switch, optical limiting, optical information storage, optical communication and the like. The 2,7-di(triphenylamine diamine) spirobifluorene provided by the invention can emit blue fluorescence of 445nm under the excitation of laser of 800nm, and has the fluorescence quantum yield reaching 87 percent. The 2,7-di(triphenylamine diamine) spirobifluorene is applied to biological cell molecular markers in two-photon fluorescence microscope and imaging, and is capable of reducing the autofluorescence background of some organisms in microscope and imaging.
Description
Technical field
The invention belongs to material science, particularly spiral shell two compound of fluorene class 2,7-bis-(triphenylamine base) spiral shell two fluorenes is preparing the application in Oragnic Two-photon Absorption Materials and photon induced blue fluorescent material.
Background technology
Along with the arrival of the information age centered by photonics, the photoelectric material with the super fast response of specific information processing capacity becomes the main body of Future Information Materials.In the development of photoelectron technology, nonlinear optics (Nonlinera Optics, NLO) serves crucial effect.Organic non linear optical material, compared with inorganic materials, has many distinguishing features, as advantages such as nonlinear optical coefficients are large, fast response time, optical damage threshold are high, direct current specific inductivity is low.Organic two-photon absorption refers to: under the exciting of pulse laser, and the organic molecule with large π-electron conjugated system and larger transition dipole distance can make the process of transition of electron to high level of its frontier orbit by simultaneously stability two photons.
Oragnic Two-photon Absorption Materials has larger application potential in fields such as all-optical switch, optical Limiting, laser device, laser ranging, optical communication, optical information storage and bioluminescence imagings.But such Oragnic Two-photon Absorption Materials often requires that molecule has large nonlinear optical coefficients concurrently, good light transmission, the multiple performance such as high thermostability.And take into account these requirements simultaneously and often have suitable difficulty, this just seriously limits material application in practice.The reason that each performance is difficult to complex optimum is just that this serial performance requriements is not isolated, even if incomplete contradiction is also close association and conditions each other each other.Such as, the nonlinear factor of most organic chromophores is larger, the maximum absorption wavelength (λ of organic chromophore
max) also can increase, namely there is " red shift ", cause the transparency range of molecule to narrow. thereuponHere it is so-called " non-linear-light transmission contradiction ".In addition, extend conjugated bridge length and can carry high molecular non-linear value, but also can fall low molecular thermostability simultaneously, namely there is " non-linear-thermostability contradiction ".Most heat decomposition temperature (the T of chromophore of current use
d) not high.Under maintenance device long lifetime necessary high poling temperature and device fabrication temperature, these chromophores are likely because decomposing, distilling or oxidized and inactivation, and therefore the thermostability of organic chromophore is also problem anxious to be resolved in organic chromophore design.If from a certain, two specific performance indexs required by device practicality, current result of study can meet the demands.But really do not develop the material system that simultaneously can meet all real requirements so far.
For some time in the past, the development of red light-emitting and the sharp two-photon absorption compound penetrated is very rapid, by contrast, the report of blue light emitting compound is less, but it micro-at two-photon fluorescence with the biomass cells molecule marker in imaging and in the autofluorescence reducing in organism fluorescence microscopy and imaging highly significant.
2,7-bis-(triphenylamine base) spiral shell two fluorenes, its structural formula is:
Describe in existing document 2,7-bis-(triphenylamine base) spiral shell two fluorenes synthesis and property application (1, J.Am.Chem.Soc., 2012,134,15402-15409; 2, Optical Materials, 2011,33,755 – 758; 3, J.Phys.Chem.C, 2011,115,19890 – 19896; 4, J.Phys.Chem.C, 2012,116,11584-11588.), its application is mainly used in the field such as electroluminescent, electrochemiluminescence.
Summary of the invention
The object of this invention is to provide the novelty teabag of spiral shell two compound of fluorene class 2,7-bis-(triphenylamine base) spiral shell two fluorenes, namely at the new opplication of Material Field.
Relate to 2,7-bis-(triphenylamine base) spiral shell two fluorenes and prepare the application in Oragnic Two-photon Absorption Materials.
Also relate to the application of 2,2,7-bis-(triphenylamine base) spiral shell two fluorenes in the blue fluorescent material that preparation is photon induced.
The preparation method of 2,7-bis-(triphenylamine base) provided by the invention spiral shell two fluorenes is: successively by 2,7 dibromo spiral shell two fluorenes, 4-boric acid triphenylamine, palladium, triphenylphosphine, salt of wormwood joins in flask, when passing into nitrogen, inject tetrahydrofuran (THF), back flow reaction, room temperature is cooled to after question response terminates, except desolventizing, gained solid carries out column chromatography (300-400 order silica gel), namely obtains target product 2,7-bis-(triphenylamine base) spiral shell two fluorenes, concrete reaction equation is:
The invention has the beneficial effects as follows: 1, provided by the invention 2,7-bis-(triphenylamine base) spiral shell two fluorenes is used as Oragnic Two-photon Absorption Materials, there is the advantage of high non-linearity and thermostability and good transparency etc., can be applicable to the optical material fields such as all-optical switch, optical Limiting, optical information storage, optical communication; 2, provided by the invention 2,7-bis-(triphenylamine base) spiral shell two fluorenes is under 800nm laser excitation, the blue-fluorescence of 445nm can be sent and the fluorescence quantum yield had up to 87%, it is micro-with the biomass cells molecule marker in imaging that this spiral shell two fluorene compound is applied to two-photon fluorescence, can reduce some organism micro-with the autofluorescence background in imaging.
Accompanying drawing explanation
Fig. 1 is 2,7-bis-(triphenylamine base) spiral shell two fluorenes
1h NMR.
Fig. 2 is the UV, visible light extinction spectrum figure of 2,7-bis-(triphenylamine base) spiral shell two fluorenes.
Fig. 3 is the fluorescence spectrum figure of 2,7-bis-(triphenylamine base) spiral shell two fluorenes.
Fig. 4 is differential thermal and the thermogravimetric analysis figure of 2,7-bis-(triphenylamine base) spiral shell two fluorenes.
Fig. 5 is the redox potential figure of 2,7-bis-(triphenylamine base) spiral shell two fluorenes.
Fig. 6 is the two photon absorption cross section Z-scintigram of 2,7-bis-(triphenylamine base) spiral shell two fluorenes.
Fig. 7 is the two-photoninduced fluorescence figure of 2,7-bis-(triphenylamine base) spiral shell two fluorenes.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
The preparation of 2,7-bis-(triphenylamine base) spiral shell two fluorenes:
Successively by 2 of 94.5mg, 7 dibromo spiral shell two fluorenes, the 4 boric acid triphenylamines of 0.129g, the palladium of 20mg, the triphenylphosphine of 22.5mg, the salt of wormwood of 0.265g joins in 100mL round-bottomed flask, plugs reflux condensing tube, nitrogen protection.Inject 20mL tetrahydrofuran (THF), backflow 36h.Stopped reaction, be cooled to room temperature, except desolventizing, gained solid carries out column chromatography (300-400 order silica gel), and leacheate is the mixed solution of sherwood oil and ethyl acetate, and wherein the volume ratio of sherwood oil and ethyl acetate is 50:1, obtain target product 2,7-bis-(triphenylamine base) spiral shell two fluorenes, products weight is 107mg, and productive rate is 66%.
Detection display 2,7-bis-(triphenylamine base) spiral shell two fluorenes
1h NMR data are as follows:
1H NMR(400MHz，CDCl3，δ)：7.91(m，4H)，7.62(d，2H，J=8.0)，7.40(d，2H)，7.33(d，4H，J=8.6)，7.31(t，8H)，7.15(t，2H)，7.08(d，8H)，7.03(t，8H)，6.91(s，2H)，6.84(d，2H)。
The performance test of 2,7-bis-(triphenylamine base) spiral shell two fluorenes
1, UV, visible light extinction spectrum test
2,7-bis-(triphenylamine base) spiral shell two fluorenes is dissolved in Isosorbide-5-Nitrae-dioxane, toluene, methylene dichloride, tetrahydrofuran (THF), acetonitrile, ethanol, methyl-sulphoxide and DMF respectively, is mixed with 1 × 10
-5the mixed solution of mol/L, tests its UV, visible light extinction spectrum.Detected result as shown in Figure 2.As we can see from the figure, the maximum absorption wavelength of compound in all kinds of SOLVENTS is all less than 400nm, and cutoff wavelength is all less than 424nm, illustrates that 2,7-bis-(triphenylamine base) spiral shell two fluorenes has the good transparency.
2, fluorescence spectrum test
2,7-bis-(triphenylamine base) spiral shell two fluorenes is dissolved in Isosorbide-5-Nitrae-dioxane, toluene, methylene dichloride, tetrahydrofuran (THF), acetonitrile, ethanol, methyl-sulphoxide and DMF respectively, is mixed with 1 × 10
-5the mixed solution of mol/L, tests its fluorescence spectrum.Fluorescence spectrum figure as shown in Figure 3.As we can see from the figure, the maximum emission peak of compound at about 440nm, and obviously can see that emission maximum peak position is along with solvent polarity increase red shift gradually.
3, THERMAL STABILITY
2,7-bis-(triphenylamine base) spiral shell two fluorenes is carried out on Shimadzu DT-40 type thermogravimetric analyzer DTA and TGA test, test condition is: ceramic crucible (uncovered), nitrogen atmosphere, and airflow rate is 30mL/min, and heating rate is 10.0 DEG C/min.Test result as shown in Figure 4.As can be seen from Figure 4,2,7-bis-(triphenylamine base) spiral shell two fluorenes has good thermostability, its decomposition temperature T
dbe 501 DEG C, second-order transition temperature is 281 DEG C.
4, redox potential
Select the new methylene dichloride steamed as solvent, tetra-n-butyl amine perchlorate (purity is 99 ﹪) is as ionogen, and the substrate solution of preparation 0.1mol/L concentration, sweep velocity is 0.1v/s, and the scanning number of turns is 4, and sample concentration is 10
-3mol/L, mercurous chloride electrode is reference electrode, and platinum carbon dioxide process carbon electrode is working electrode, and platinum plate electrode is supporting electrode, and each electrode strictly processes before use as requested.During test, first scan blank solution (i.e. 0.1mol/L electrolyte solution), after system stability, then 2,7-bis-(triphenylamine base) spiral shell two fluorenes is joined in electrolyte solution, scan again after stable.Redox potential figure as shown in Figure 5.As can be seen from the figure, the oxidizing potential of 2,7-bis-(triphenylamine base) spiral shell two fluorenes is 0.922V.
5, two photon absorption cross section test
2,7-bis-(triphenylamine base) spiral shell two fluorenes is dissolved in tetrahydrofuran (THF), is mixed with 1.0 × 10
-2the mixed solution of mol/L.Use the femto-second laser of 800nm wavelength, light intensity is 70mW, and recording two photon absorption cross section is 63449GM, illustrates that 2,7-bis-(triphenylamine base) spiral shell two fluorenes has very strong two-photon absorption ability.Two photon absorption cross section Z-scintigram the results are shown in Figure shown in 6.
6, photon induced fluorometric investigation
2,7-bis-(triphenylamine base) spiral shell two fluorenes is dissolved in tetrahydrofuran (THF), is mixed with 8 × 10
-5the mixed solution of mol/L, uses its two-photon fluorescence spectrum of laser testing of 800nm wavelength.Two-photon fluorescence spectrogram is shown in Fig. 7.As we can see from the figure, the maximum emission peak of compound is at about 445nm.Fluorescence quantum yield is 87%, and fluorescence quantum yield is the important parameter characterizing fluorescent material, illustrates that it has good luminescent properties.
Claims (2)
1.2,7-bis-(triphenylamine base) spiral shell two fluorenes is preparing the application in Oragnic Two-photon Absorption Materials.
The application of 2.7-bis-(triphenylamine base) spiral shell two fluorenes in the blue fluorescent material that preparation is photon induced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210591635.4A CN103013498B (en) | 2012-12-29 | 2012-12-29 | Application of 2,7-di(triphenylamine diamine) spirobifluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210591635.4A CN103013498B (en) | 2012-12-29 | 2012-12-29 | Application of 2,7-di(triphenylamine diamine) spirobifluorene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103013498A CN103013498A (en) | 2013-04-03 |
| CN103013498B true CN103013498B (en) | 2015-02-18 |
Family
ID=47962621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210591635.4A Expired - Fee Related CN103013498B (en) | 2012-12-29 | 2012-12-29 | Application of 2,7-di(triphenylamine diamine) spirobifluorene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103013498B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961643A (en) * | 2015-06-08 | 2015-10-07 | 南京工业大学 | Hole transport material applied to solar cell |
| CN106220514A (en) * | 2016-07-21 | 2016-12-14 | 上海师范大学 | A kind of Spirobifluorene compound containing the tert-butyl group and preparation thereof and application |
| CN110540524B (en) * | 2019-08-15 | 2020-09-18 | 西安交通大学 | D-A-D type fluorescent small molecule based on pyrazine, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6476265B1 (en) * | 1997-09-05 | 2002-11-05 | Covion Organic Semiconductors Gmbh | Method for producing aryl oligoamines |
| CN1546446A (en) * | 2003-12-15 | 2004-11-17 | 中国科学院上海光学精密机械研究所 | Fluorene derivative and application thereof |
| CN102167971A (en) * | 2011-03-02 | 2011-08-31 | 北京大学 | Blue-fluorescence luminescent material and application thereof |
| CN102617466A (en) * | 2011-12-31 | 2012-08-01 | 上海师范大学 | Top-bottom asymmetrical tert-butyl spirobifluorene compound |
| CN102633610A (en) * | 2011-12-31 | 2012-08-15 | 上海师范大学 | 'Vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on fluorene loop and preparation method and application thereof |
| CN102766084A (en) * | 2011-12-31 | 2012-11-07 | 上海师范大学 | Vertically asymmetrical methyl spirobifluorene compound |
-
2012
- 2012-12-29 CN CN201210591635.4A patent/CN103013498B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6476265B1 (en) * | 1997-09-05 | 2002-11-05 | Covion Organic Semiconductors Gmbh | Method for producing aryl oligoamines |
| CN1546446A (en) * | 2003-12-15 | 2004-11-17 | 中国科学院上海光学精密机械研究所 | Fluorene derivative and application thereof |
| CN102167971A (en) * | 2011-03-02 | 2011-08-31 | 北京大学 | Blue-fluorescence luminescent material and application thereof |
| CN102617466A (en) * | 2011-12-31 | 2012-08-01 | 上海师范大学 | Top-bottom asymmetrical tert-butyl spirobifluorene compound |
| CN102633610A (en) * | 2011-12-31 | 2012-08-15 | 上海师范大学 | 'Vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on fluorene loop and preparation method and application thereof |
| CN102766084A (en) * | 2011-12-31 | 2012-11-07 | 上海师范大学 | Vertically asymmetrical methyl spirobifluorene compound |
Non-Patent Citations (3)
| Title |
|---|
| Improved Nonlinearity-Transparency Thermal Stability Trade-Off with Spirobifluorene-Bridged Donor-π-Acceptor Chromophores;Haibo Xiao等;《ORGANIC LETTERS》;20120410;第14卷(第20期);5282-5285 * |
| Spirosilabifluorene linked bistriphenylamine: Synthesis and application in hole transporting and two-photon fluorescent imaging;Haibo Xiao等;《Dyes and Pigments》;20060119;第73卷;224-229 * |
| 基于杂环的几种强双光子吸收材料的制备及性能研究;刘常琳;《山东轻工业学院硕士学位论文》;20100601;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103013498A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deng et al. | Enabling Förster resonance energy transfer from large nanocrystals through energy migration | |
| Singh et al. | Structural, Thermal, and Fluorescence Properties of Eu (DBM) 3Phen x Complex Doped in PMMA | |
| Ren et al. | Enhanced emission efficiency and excited state lifetime due to restricted intramolecular motion in silole aggregates | |
| Li et al. | Highly solvatochromic fluorescence of anthraquinone dyes based on triphenylamines | |
| Feng et al. | Photochromic thiophene oligomers based on bisthienylethene: syntheses, photochromic and two-photon properties | |
| Lanke et al. | Aggregation induced emissive carbazole-based push pull NLOphores: synthesis, photophysical properties and DFT studies | |
| Heek et al. | Synthesis and Optical Properties of Water‐Soluble Polyglycerol‐Dendronized Rylene Bisimide Dyes | |
| Ghouili et al. | Synthesis, crystal structure and spectral characteristics of highly fluorescent chalcone-based coumarin in solution and in polymer matrix | |
| Xia et al. | Multifunctional diarylamine-substituted benzo [k] fluoranthene derivatives as green electroluminescent emitters and nonlinear optical materials | |
| Tu et al. | Advances in pure organic mechanoluminescence materials | |
| Yang et al. | Facile access to extremely efficient energy-transfer pairs via an unexpected reaction of squaraines with ketones | |
| Yang et al. | Synthesis, spectroscopic characterization, one and two-photon absorption properties, and electrochemistry of truxene π-expanded BODIPYs dyes | |
| CN103013498B (en) | Application of 2,7-di(triphenylamine diamine) spirobifluorene | |
| Xu et al. | High-performance two-photon absorption luminophores: large action cross sections, free from fluorescence quenching and tunable emission of efficient non-doped organic light-emitting diodes | |
| Zhang et al. | Enabling DPP derivatives to show multistate emission and developing the multifunctional materials by rational branching effect | |
| Liang et al. | New Anthracene Derivatives as Triplet Acceptors for Efficient Green‐to‐Blue Low‐Power Upconversion | |
| Gudeika et al. | Donor and acceptor substituted triphenylamines exhibiting bipolar charge-transporting and NLO properties | |
| Dar et al. | Nanotechnology-Assisted, Single-Chromophore-Based White-Light-Emitting Organic Materials with Bioimaging Properties | |
| Chen et al. | Immensely enhanced color-adjustable upconversion fluorescence in electron donor-acceptor exciplex chromophores doped with fluorescent emitters | |
| Yi et al. | Triphenylethylene benzimidazole derivatives with aggregation-induced emission (AIE) characteristics: An effect of the aryl linker and application in cell imaging | |
| CN113527185A (en) | D-Pi-A type tetraphenyl vinyl ethynyl phenyl substituted pyridine conjugated light-emitting small molecule and synthetic method thereof | |
| Wang et al. | Triphenylamine pyridine acetonitrile fluorogens with green emission for pH sensing and application in cells | |
| Chen et al. | Rationalize the roles of electron donating-withdrawing groups in the impacts on solvatochromism, nonlinear optics, and electroluminescence devices | |
| Jih et al. | Role of π-bridge and strong solid-state emission in triphenylamine-benzothiazole based nonlinear optical dyes | |
| Yu et al. | Tetraazatetraoxodecacene and tetraazatetrathiodecacene: synthesis, crystal structures, linear and third-order nonlinear optical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150218 Termination date: 20171229 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |