CN103087000B - Oxadiazole-triphenylamine-anthracene conjugated molecule with three-photon fluorescence characteristic - Google Patents
Oxadiazole-triphenylamine-anthracene conjugated molecule with three-photon fluorescence characteristic Download PDFInfo
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- CN103087000B CN103087000B CN201310017647.0A CN201310017647A CN103087000B CN 103087000 B CN103087000 B CN 103087000B CN 201310017647 A CN201310017647 A CN 201310017647A CN 103087000 B CN103087000 B CN 103087000B
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- oxadiazole
- triphenylamine
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Abstract
The invention discloses an oxadiazole-triphenylamine-anthracene conjugated molecule with a three-photon fluorescence characteristic. The oxadiazole-triphenylamine-anthracene conjugated molecule is characterized by being a dendritic conjugated molecule consisting of 2,5-diphenyl oxadiazole, triphenylamine and anthracene. The oxadiazole-triphenylamine-anthracene conjugated molecule disclosed by the invention has strong intramolecular charge transfer, generates bright three-photon fluorescence under the excitation of femtosecond laser, is strong in fluorescence and high in quantum efficiency, and has important application value in the fields of multi-photo fluorescence microimaging and ultrahigh-density three-dimensional light storage.
Description
Technical field
The invention discloses a kind of three-photon fluorescent Te oxadiazole-triphenylamine-anthracene conjugated molecule that has, it is characterized in that: it is the dendriform conjugated molecule by 2,5-bis-Ben oxadiazole, triphenylamine and anthracene composition.Oxadiazole-triphenylamine-anthracene compounds of the present invention exists very strong intramolecular charge to shift, and excites the bright three-photon fluorescent of lower generation at femtosecond laser.There is important using value at multiphoton fluorescence micro-imaging and super-high density three-dimensional light field of storage.
Background technology
Three-photon fluorescent excitation wavelength adopts penetrativity is stronger in biological tissue infrared laser as excitation light source, can avoid the fluorescent bleach problem in common fluorescence imaging and the photic malicious problem to biomass cells.And linear absorption and the Rayleigh scattering of biological tissue to this optical band is all smaller, can on the three-dimensional any site of the degree of depth, cause photophysical process and photoprocess, greatly improve transmission depth and investigation depth.Compared with two-photon fluorescence, three-photon fluorescent has higher room and time resolving power.Three-dimensional super-high density optical storage, take three-photon fluorescent molecule as medium, can realize the storage of super-high density body, improves immunity from interference between layers, and theoretic resolution limit can reach molecular scale.Take three-photon fluorescent molecule as medium, multiphoton fluorescence micro-imaging technique has ultrahigh resolution, can be used to Real Time Observation viable cell, obtains the living tissue 3-D view of deep layer, and in research viable cell, the real-time unit molecule of chemical process shows.
Summary of the invention
Goal of the invention: the object of this invention is to provide a kind of three-photon fluorescent performance oxadiazole-triphenylamine-anthracene compounds that has.
Technical scheme: the technical solution used in the present invention is a kind ofly to have efficient three-photon fluorescent Te oxadiazole-triphenylamine-anthracene dendriform conjugated molecule ， oxadiazole-triphenylamine-anthracene conjugated molecule and be made up of following structural formula:
The above oxadiazole-triphenylamine-anthracene conjugated molecule of Yi, is characterized in that: it is by fluorophor 2, and 5-bis-Ben oxadiazole, triphenylamine and anthracene nucleus are connected by two key conjugation, optimum combination and obtaining.The proportion of composing of fluorophore is anthracene: triphenylamine: oxadiazole=1:2:4
The synthetic method of oxadiazole-triphenylamine-anthracene conjugated molecule can be referring to the statement of embodiment.
Beneficial effect: compared with prior art, its remarkable advantage is in the present invention:
Oxadiazole-triphenylamine-anthracene dendriform conjugated molecule 9 of the present invention, two { the 4-{N of 10-, N-bis-{ 4-{4-[5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole-2] styryl } phenyl } amino } styryl } anthracene, be by fluorophor 2,5-bis-Ben oxadiazole, triphenylamine and anthracene nucleus are connected by two key conjugation, optimum combination and obtaining, the proportion of composing of fluorophore is anthracene: triphenylamine: oxadiazole=1:2:4.Oxadiazole-triphenylamine-anthracene dendriform conjugated molecule of the present invention exists very strong intramolecular charge to shift, excite the bright three-photon fluorescent of lower generation at femtosecond laser, fluorescence is strong, quantum yield is high, has important using value at multiphoton fluorescence micro-imaging and super-high density three-dimensional light field of storage.
Embodiment
By the following examples the present invention is described in further detail:
Embodiment 1. oxadiazoles-triphenylamine-anthracene dendriform conjugated molecule 9,10-two { 4-{N, N-bis-{ 4-{4-[5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole-2] styryl } phenyl } amino } styryl } preparation method of anthracene
(1) anthracene-9,10-two (methylene radical etherophosphoric acid) and 4-[N, N-bis-(4-iodine substituted phenyl) amino] phenyl aldehyde 1:2.2 reaction in molar ratio, obtain 9,10-two { 4-[N, N-bis-(4-iodophenyl) amino] styryl } anthracene (A).
Take anthracene-9,10-bis-(methylene radical etherophosphoric acid) 0.12g(0.25mmol) be dissolved in 5mL dry THF, under nitrogen protection, drip and be dissolved with 4-[N, N-bis-(4-iodophenyl)] phenyl aldehyde 0.29g(0.55mmol) 10mL THF solution.Slowly splash into and be dissolved with potassium tert.-butoxide 0.34g(3.00mmol) 10mL THF solution, room temperature reaction 24h.Suction filtration, dry, recrystallization obtains orange red solid (A), productive rate 70%.
Analyze gained compd A:
1H?NMR(300MHz,CDCl
3)δ:8.39(d,J＝8.70Hz,4H),7.87(d,J＝16.30Hz,4H),7.58(d,J＝7.30Hz,8H),7.47(d,J=6.60Hz,4H),7.14(d,J＝7.90Hz,4H),6.91(d,J＝7.70Hz,8H);
The structural formula of compound obtaining is
(2) under nitrogen protection and anhydrous and oxygen-free condition, by 9, two { the 4-[N of 10-, two (4-iodophenyl) amino of N-] styryl } anthracene (A) 0.24g (0.20mmol) and 2-(4-tert-butyl-phenyl)-5-(4-ethenylphenyl)-[1, 3, 4]-oxadiazole 0.29g (0.96mmol) are dissolved in respectively anhydrous N, in N-N,N-DIMETHYLACETAMIDE, dropping is dissolved with anhydrous phosphoric acid potassium 0.24g (1.12mmol), the anhydrous N of three (o-methyl-phenyl-) phosphine 0.049g (0.16mmol) and palladium 0.018g (0.08mmol), N-dimethylacetamide solution, after magnetic agitation 0.5h, be warming up to 130 ℃, back flow reaction 96h.After reaction finishes, reaction solution is filtered in methyl alcohol, separated out dun solid, suction filtration, with methylene chloride/methanol mixed solvent recrystallization, purifies with column chromatography method, and gradient elution, obtains garnet solid (B), productive rate 74%.
Analyze gained compd B:
1H?NMR(300MHz,CDCl
3)δ:8.45(dd,J
1=3.24Hz,J
2=3.36Hz,4H),8.14(dd,J
1=8.43Hz,J
2=8.28Hz,16H),7.92(d,J＝16.53Hz,4H),7.68(dd,J
1=8.46Hz,J
2=5.64Hz,10H),7.57(dd,J
1=8.49Hz,J
2=8.31Hz,20H),7.23(dd,J
1=3.66Hz,J
2=6.57Hz,12H),7.12(d,J＝16.08Hz,4H),6.96(d,J＝15.42Hz,4H)
The structural formula of compound obtaining is
Table 1 embodiment compound 9,10-two { 4-{N, N-bis-{ 4-{4-[5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles
-2] styryl } phenyl } amino } styryl } the three-photon optical property (solvent is THF) of anthracene
Note:
represent the position of linear absorption spectrum,
represent the position of single photon fluorescence peak, σ
3PA10
-79cm
6s
2be illustrated in 1300nm femtosecond laser and excite the lower Three-photon absorption cross section (unit 10 measuring by nonlinear transmission method
-79cm
6s
2),
be illustrated in the position that 1300nm femtosecond laser excites lower three-photon fluorescent peak, excitation light source is titanium jewel fs-laser system, repetition rate 1KHz, and 80fs pulsewidth, wavelength is 1300nm.Solvent is THF.
Claims (1)
1. there is oxadiazole-triphenylamine-anthracene conjugated molecule of three-photon fluorescent spy property, it is characterized in that stated oxadiazole-triphenylamine-anthracene conjugated molecule is made up of following structural formula:
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| CN103524404B (en) * | 2013-10-23 | 2015-03-18 | 东南大学 | Pyridine-triphenylamine-anthracene conjugated molecule with aggregation-induced emission property and preparation method thereof |
| CN103896825B (en) * | 2014-04-17 | 2015-11-11 | 东南大学 | A kind of 9,10-diarylethene base anthracene aggregation-induced emission molecule and preparation method thereof |
| CN103999853B (en) * | 2014-06-11 | 2015-07-22 | 中国农业大学 | Application of fluorescence arborization nanometer macromolecule in preparing drug carrier |
| CN104531135B (en) * | 2014-12-17 | 2016-04-13 | 东南大学 | Er Ben oxadiazole-naphthalimide fluorescent probe and application thereof |
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| CN101081978A (en) * | 2007-06-22 | 2007-12-05 | 东南大学 | Multi-branched oxdiazole two-photon pump fluorescent material and preparation method thereof |
| CN101368095A (en) * | 2008-09-24 | 2009-02-18 | 东南大学 | Aromatic heterocyclic three-photon fluorescent macromolecule and preparation method thereof |
| CN101481609A (en) * | 2009-01-20 | 2009-07-15 | 东南大学 | Symmetrical multiphoton pump luminescent material and preparation thereof |
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